AGC Book 20% Cyan Karl Fischer Titration

GTP Brochure

Good Titration Practice™ in Karl Fischer Titration

EDITORIAL

Dear Reader METTLER TOLEDO has an excellent knowledge in any kind of moisture and water content determination from % to ppm. It is of crucial importance to select the right analytical method in order to obtain reliable results that ensure quality and properties of the products in a multitude of industries. Karl Fischer titration is the method of choice for water content determination. With the new generation of METTLER TOLEDO compact volumetric and coulometric Karl Fischer Titrators V20/V30, C20/C30 and Excellence combined general and volumetric KF titrators T70 and T90, water determination has reached an unrivaled level of simplicity and security. This helps you to perform your daily tasks in the most optimal way. In this brochure a specific focus is put on how to perform the Karl Fischer titration analysis the correct way. We would like to introduce this to you as part of ‘Good Titration PracticeTM (GTP) in Karl Fischer titration. This brochure comprises detailed background information and recommendations about: • • • • • Chemistry and control of the Karl Fischer titration Practical tips and hints on sample preparation and instrument operation Measures to optimize accuracy and precision of the water determination Selection of the optimal method for water determination of your specific sample Trouble shooting recommendations if results do not coincide with the expectations

This GTP brochure in combination with the application brochure 39 should serve you as powerful tools for trouble-free water determination throughout the whole lifetime of your METTLER TOLEDO KF titrator. We wish you great success and enjoyment

Hans-Joachim Muhr Market Support Manager BA Titration

Rolf Rohner Marketing Manager BA Titration

...............................................16 3....................................4........18 3.........33 4..............................................1 Volumetric KF reagents.........................8 2........................4 Polarization current and end point..2 Two-component KF reagent .......11 2.................................................................................................13 3...................................1 The influence of atmospheric humidity (drift determination) .......................................................................................2 Working with the coulometric KF instruments .............5 Application tips ...............................................................................................................................3 Secure draining and filling of the titration cell: SOLVENT MANAGER............................................................................................2......................................................................................................... The Karl Fischer titration...4 Control parameters in the volumetric KF titration ...................2 Stoichiometry of the coulometric KF rection .10 2....................22 3....3 Stirring speed and dispersion of the volumetric KF titrant........2......1 KF coulometry ................4 Concentration determination with pure water................4........................1...................................1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration ..........9 2..2 When do you have to replace the electrolyte? ....................................24 4..................................1 Titration stand .................6 General recommendations ...20 3..........................................................................................................................................2..............................................................................4.....................................................1...3 Concentration determination with Water Standard 10......................................3 The Cautious start .............................4 Generator electrode without diaphragm ..........................................................3...........5 Karl Fischer reagents with ethanol ..........................5 The solvent.................................26 4......................................8 2...2 Coulometric KF analysis...................2 Concentration determination with di-sodium tartrate dihydrate.................9 2............................12 3 Titration control and end point determination.19 3.0 mg/g ....32 4..........................33 4....6 Termination parameters for both coulometric and volumetric KF titration.....................1 The Control Band .............................................1...3.35 4........................................................................................................................1.............5 1....................................3 Pyridine-containing reagents .................2 The minimum and maximum dosing rate ...2.......38 5 Sampling .............................4 1.........................1 One-component KF reagent .........2...............19 3...............9 2.......................37 4......18 3...........................................................................................................................................................................................................................................6.............................1...3 Iodine generation...........5 Control paramaters in the coulometric KF Analysis ...2 The Karl Fischer chemical reaction .2........7 2......2 Reaction rate .............3.........1 Filling the coulometric cell ..............21 3...............................................3 Consequences for practical applications...............29 4.......4 1.............................................................................3...................4.............................1 An historic overview ....METTLER TOLEDO Good Titration PracticeTM in KF Titration Contents 1 Fundamentals of the Karl Fischer titration ............................................39 1 .......................................................7 2............................................34 4.2 End point and polarization current...................4.......................4 Special reagents for aldehydes and ketones......28 4....................14 3................3......................................................21 3.....4.......2................4 Cleaning the coulometric KF titration cell..........3..33 4..........28 4..13 3.29 4..............................1 How often should the concentration be determined?...........................................3 Volumetric KF Titration: Titrant concentration..........................1.....................1..........11 2............................................6 2 Volumetric and Coulometric Karl Fischer Analyses ..................................................................................13 3...1 Indication ...........................................................36 4.....................5 Limitations for the use of the cell without diaphragm................................................................................5 Cleaning the measuring electrode .......................................16 3........1.................................................2..........................................26 4...........2.....................................1 Principle of bipotentiometric indication ...26 4..............7 2........27 4...........................6 Dissolving capacity of the solvent ..........2.............................................................................................................................................2 The drift .......8 2...........19 3............1................

..............................................................4 Manual Karl Fischer drying oven..............2................1 Solid samples.............................................................2..1..................................................72 10 Troubleshooting ....................2 Volumetric Karl Fischer Titration ................................................................78 11............................................................................................................1 Resolution and detection limit .................................58 7........58 7.........................................................6.........1.......1 Organic Chemicals.......1 Internal extraction ....................................................................................................................................................................................................................................70 9.................43 6........................49 7.............78 11........................................4....3 Titration Methods ...5 Technical natural products .............................................................................................5 Additional literature ...............................................................4 Technical products ..........4.......83 11..........................80 11...................................................................................2 Storing the sample ..3 Reaction with iodine .......................................59 7.......................................................1..................4.........................................................2 Inorganic chemicals ....................................................................................87 11.........1 Taking the sample....................62 8 Measurement results .................47 7.....................................................2 Side reactions ..................................................................................................86 11...........................48 7.............................................4 Lyophilized substance in septum bottles...2 External extraction ............................................................................................................................................................................55 7........................................................................58 7...............................................................................................57 7............................................................................................................................................................................................................6.6............................................86 11.......73 10.................77 11..............................81 11............2 Reaction with water...........4.........................................................71 9............1............................................................................1 Organic and inorganic chemicals ...............................60 7..86 11................................................................................................43 6.............2 Measurement accuracy...................................................................1 Volumetric methods .................2 Coulometric methods ...................................6 References.............77 11.....................................5 Accessories for sample input ..70 9..............2 Foods and technical products .....................................................................................................................................3 External dissolution ................................................2 Liquid samples ...............................39 5.................................1 Principle ...........................................................................................................................................................................1........................METTLER TOLEDO Good Titration PracticeTM in KF Titration 5................................85 11...................2 Solids: Sample input ........2.......................................................2 Purge gas........89 12 Appendix .........3 Repeatability ..............3 Liquids: Characteristics ........................4 Sample preparation and input .............3.................................40 6 Sample addition .......................................................................................................................5 STROMBOLI automatic oven sample changer ...........................87 11......................................3 Amount of sample ...90 2 .........79 11.....................inorganic ......................79 11........1...............6..............68 9 Interferences ......................................80 11.................................67 8......................................................................................73 10...75 11 Karl Fischer Titration: The Method at a Glance ..79 11..............................................39 5...................................................................................1 Effects of temperature...........................3 Technical products – organic .6.............................6 Food .3.....................1 Reaction with methanol.......................................................................88 11.............................................................1 Solids: Characteristics.............................................................................................................6 Determination using the drying oven .......4...............4 Liquids: Sample input...................................................................................................................4 Example: reevaluation of side reactions ...........................5 Determination of water in gases ..........................................................4......................71 9.............................................1 Liquid samples ..............................................67 8....................................1 Coulometry.....................................................................2 Solid samples................................................83 11.................................2...70 9.....................................................................45 7 Release of water from the sample .........87 11...........................................................3 Procedure....................................................................................................71 9............................................................................................54 7................77 11...................................67 8.......................................................................................................

................................6....................................................................6........................................3 For samples insoluble in methanol or ethanol......................5 For acids and bases (pH value) ...........98 13.....................98 13.......98 13.........90 12.........................................92 12........3 Reagents for coulometry: ............4 For ketones and aldehydes..........................................5 Water Standards for Karl Fischer volumetric titration..............6 Titrants and solvents for volumetric analysis ..................98 3 ..............................6............................1 Formula for the external extraction .......95 12.4..................................................6.......................................4 Reagents and solvents for coulometric analysis ...4.............................................................1 One-component reagent ...................................96 12...5 For acids and bases (pH value) ...95 12......91 12...............................................................................4.2 Two-component reagent: .................................................................................3 For samples that are insoluble in methanol or ethanol ................2 For samples poorly soluble in methanol or ethanol...3 Standards for Karl Fischer coulometry..................................................................4.....................4..................1 For samples that are soluble in methanol or ethanol .............2 For samples that are poorely soluble in methanol or ethanol .95 12.......6...........................................................................................................................................................................94 12..................................93 12................................................................................4 Safety data for the KF-components and auxiliary solvents: .............2 Formula for the external dissolution ...........1 For samples soluble in methanol or ethanol ................4 For ketones and aldehydes...................................91 12.............................93 12...97 13 Hazards and waste disposal tips ..95 12........98 13.......................................96 12........................................92 12.........92 12.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12....

titrant specific standard parameters and LEARN titration. First fully automatic KF titration with laboratory robots (METTLER DL18 and ZYMARK). Water standards (10. promoted by publications by E. Peters and J. 2000 2001 2002 2008 4 . Introduction of the METTLER TOLEDO Titration Compact Line V20/V30 and C20/C30 Karl Fischer Instruments. S. April 1956. They replaced the DL18/35 KF Volumetric Titrators. Publication: “The Dead-Stop End Point“.J. Introduction of the METTLER TOLEDO DL32/39 KF Coulometers (generating cell with and without diaphragm). Enormous spread of the use of KF titration.Direct method”). M. Hopkinson [2]. DL37 KF Coulometer from METTLER TOLEDO.0. Pyridine-free KF reagents are commercially available. 1. Introduction of less poisonous KF reagents based on ethanolic solution. First German DIN standard for the Karl Fischer titration (DIN 51777. by G. Publication on stabilized single-component Karl Fischer reagent by E. Pyridine-containing two-component reagents and dead-stop titration instruments are commercially available. Wernimont and F.1 mg/g) with test certificate according to DIN 50049-2. and solvent dispensing and removal. 0. Publication: Coulometric Karl Fischer Titration by A. 1959 1960 1970 1980 1984 1985 1989 1990 1995 1997 1998 New DV705 KF Titration Stand with very low drift value (< 2μg/min) for the METTLER TOLEDO DL53/55/58. and DL67/70ES/77 Titrators Introduction of the METTLER TOLEDO DL31/DL38 KF Titrators with dedicated fuzzy logic control. Eberius [3].METTLER TOLEDO Good Titration PracticeTM in KF Titration 1 Fundamentals of the Karl Fischer titration 1. Use of Karl Fischer method spreads.3 First titrator (METTLER TOLEDO DL55) with online curves E = f(t) and V = f(t) for Karl Fischer titration. Improved METTLER TOLEDO DO307 KF Manual Drying Oven. Jungnickel. Automatic KF titration instruments with piston motorized burettes.Boyd [4].5% and 1%. D. First diaphragm-less cell for coulometric KF titration. First coulometric KF titration instruments are commercially available. respectively. Meyer and C. “Testing of mineral oil hydrocarbons and solvents: Determination of water content according to Karl Fischer . Solid KF Oven Standards with water contents of 5.1 1935 1943 1950 1952 1955 1956 An historic overview Publication: "Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern" by Karl Fischer [1]. L. Introduction of the METTLER TOLEDO STROMBOLI KF Oven Sample Changer. METTLER TOLEDO RONDO Sample Changer with Karl Fischer Kit for automated KF volumetric determination. DO185 Drying Oven for the DL18 Karl Fischer Volumetric Titrator.0. First microprocessor controlled KF titrator (METTLER DL18) with automatic drift compensation.

. Smith. the more methyl sulfite is formed by the capture of protons. it is necessary to neutralize the acids that are formed during the process (HI and H2SO4). Py•SO3 + CH3OH → 2 Py-H+I– + Py•SO3 – Py-H+CH3SO4 According to these equations. In order to achieve an equilibrium shift to the right. Bryanz and Mitchell [6] formulated a two-step reaction: 1. i. the reaction between iodine and water takes place in the stoichiometric ratio of 1:1. C. Bunsen [5]: Karl Fischer discovered that this reaction could be used for water determinations in a nonaqueous system containing an excess of sulfur dioxide [1]. described by the rate constant k. and the faster the rate of the Karl Fischer reaction. In the pH range 5. Py•SO3 + H2O → 2 Py-H+I– + Py•SO3 – Py-H+HSO4 – Further studies conducted by J. W. methanol not only acts as a solvent but also participates directly in the reaction itself. it only acts as a buffering agent and can therefore be replaced by other bases. the maximum reaction rate is reached here and cannot increase further. In an alcoholic solution. but rather the methyl sulfite ion. all the sulfur dioxide is present as methyl sulfite. depends on the pH value of the medium (see graphics below) -d[I2]/dt = k • [I2] • [SO2] • [H2O] One possible explanation for the influence of pH on the reaction rate is that it is not the sulfur dioxide itself that is oxidized by iodine under the influence of water. This is formed from sulfur dioxide and methanol according to the equation: 2 CH3OH + SO2 → CH3OH2+ + CH3OSO2- The higher the pH of the solution.5.5 to 8. Methanol proved to be suitable as a solvent.2 The Karl Fischer chemical reaction I2 + SO2 + 2 H2O → 2 HI + H2SO4 The water content determination is based on the reaction described by R. At pH values above 8. Verhoff and E. Barenrecht [7] on the subject of the Karl Fischer reaction have revealed that: • • Pyridine is not directly involved in the reaction. the 5 . Karl Fischer used pyridine for this purpose. The rate of the Karl Fischer reaction. In an alcohol-free solution.e. I2 + SO2 + 3 Py + H2O → 2. I2 + SO2 + 3 Py + H2O → 2.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1. the reaction between iodine and water takes place in the stoichiometric ratio of 1:2: 1.

but also facilitated faster and more accurate titrations because imidazole buffers in a more favorable pH range than pyridine. This reagent not only replaced the toxic. and for bases: salicylic acid). in a titration. and references therein]. pungent pyridine. ROH + SO2 + RN 2. • Influence of the water content of the sample on the Karl Fischer reaction The water content of the sample also influences the H2O:I2 molar ratio. E. methoxyethanol. for instance. This. (RNH) · SO3 R + 2 RN + I2 + H2O This resulted in the general chemical equation: ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I E. → → (RNH) · SO3 R (RNH) · SO4 R + 2 (RNH)I 1. J. Experiments on the stoichiometry of the reaction showed that methanol can in fact be replaced by other alcohols (e. diethylene glycol monoethylether) [10. pH values less than 4 and greater than 8 should be avoided in practice. Scholz was also able to confirm the existence of basic methylsulfite in methanol/SO2/I2 solutions during the titration. On the basis of this knowledge. ethylene glycol monomethyl ether. 6 .g. Verhoff and E.METTLER TOLEDO Good Titration PracticeTM in KF Titration reaction rate increases due to side reactions between iodine and hydroxide or methylate ions. Seubert [9] identified methylsulfite in KF solutions with the aid of IR spectroscopy and isolated and identified methyl sulfate as the secondary product of the KF reaction. this results in a more sluggish endpoint and higher iodine consumption.3 • Consequences for practical applications Influence of pH on the Karl Fischer reaction Since the maximum rate of the Karl Fischer titration is in the pH range 5.g. Barendrecht [7] observed an increase in the titer with water contents greater than 1 mol/L. Scholz resulted in the following reaction scheme being proposed for the Karl Fischer reaction [8]: 1.g. With acidic or basic samples. ethanol. 2-propanol. In 1988.5 to 8.g. • Influence of the solvent on the Karl Fischer reaction The stoichiometry (molar ratio of H2O:I2) depends on the type of solvent: Alcoholic solvent Non-alcoholic solvent H2O:I2 = 1:1 H2O:I2 = 2:1 (e. you should adjust the pH value to the ideal range by adding buffering agents (for acids: imidazole. Studies by E. Scholz developed a pyridine-free Karl Fischer reagent with imidazole as base [8]. Methanol should therefore always be present in the minimum required amount. dimethylformamide) Studies by Eberius [3] showed that iodine and water react in the ratio of 1:1 if the percentage of methanol in the solvent is 20% or more. for determination in ketones or aldehydes).C. A. however. This improves the titer stability. If a methanol-free titrant has to be used (e. is not a serious limitation because the water concentration in the solvent is usually much less. you can use other alkohols such as. methanol) (e.

2 mg/mL for samples with a water content of less than 1000 ppm.e. The reagent is available in three different concentrations: 5 mg/mL for samples with a water content of 1000 ppm to 100%. where a solution containing iodine is added using a motorized piston burette.5% 2. i.5 mg/mL per year in a sealed bottle. The reagent can be stored for approximately two years. dissolved in a suitable alcohol.1 One-component KF reagent The titrant contains iodine. The solvent is methanol.100% Coulometric Karl Fischer Analysis Iodine is generated electrochemically during titration. 7 . Suitable for samples where water is present in trace amounts: 1 ppm .1. You can also use a methanolic solvent mixture specially adapted to the sample as the solvent. 1 mg/mL for samples with a water content of less than 200 ppm. sulfur dioxide and imidazole. is approximately 0.1 Volumetric KF reagents 2.. where iodine is generated by electrochemical oxidation in the cell The selection of the appropriate technique is based on the estimated water content in the sample: Volumetric Karl Fischer Titration Iodine is added by a burette during titration. Coulometric Karl Fischer Analysis. the decrease in concentration. The drop in titer. Suitable for samples where water is present as a major component: 100 ppm .METTLER TOLEDO Good Titration PracticeTM in KF Titration 2 Volumetric and Coulometric Karl Fischer Analyses The determination of the water content according to Karl Fischer is nowadays performed by two different techniques: – – Volumetric Karl Fischer Titration.

methanol. To improve stability. These solutions are mixed 1:1 just before use to form the one-component titrant. 2 mg/mL for samples with a water content of less than 1000 ppm. leading to higher water contents and a vanishing end point.g.4 Special reagents for aldehydes and ketones Aldehydes (R-CHO) and ketones (R-CO-R) form acetals and ketals if titrated with standard methanol-containing reagents. Solvent capacity restricted.1. Note that it may be necessary to adapt the end point value in the titration method to these reagents. Special methanol-free KF one-component reagents such as e. from Sigma-Aldrich) and e. The separation into titrant and solvent improves stability of the KF reagents. stable titer. imidazole and methanol. provided that the bottle is tightly sealed.1. dissolved in methanol. The solvent is either methanol or consists of methanol mixtures. methanol) and B (iodine. The titrant has a stable titer. High titration speed.2 Two-component KF reagent The titrant contains iodine and methanol.g. whereas the solvent contains 2-chloroethanol and trichloromethane. Both the components are very stable in storage. 8 . Reagents One-component Two-component 2. pyridine. e. One-component reagent: The titrant contains iodine. or an alcoholic mixture. This reagent is declared as “rapid”.g. One-component reagent: The titrant contains iodine. The titration takes slightly longer than with the standard KF reagent. some manufacturers also sell the titrant separated into solution A (sulfur dioxide. such as amines. dissolved in an alcohol (usually methanol). imidazole. apura® (CombiTitrant 5 Keto with CombiSolvent Keto.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. e. sulfur dioxide and pyridine. 2.1. This special reagent is also suitable for substances that react with methanol. additional water is produced and titrated at the same time. HYDRANAL® (Composite 5K and Working Medium K. titration speed slower. imidazole. The solvent contains sulfur dioxide.3 Pyridine-containing reagents Despite the existence of pyridine-free reagents. It is available in two different concentrations: • • 5 mg/mL for samples with a water content of 1000 ppm to 100%. whereas the solvent consists of sulfur dioxide and a base. Two-component reagent: The titrant contains iodine dissolved in an alcohol. reagents containing pyridine are still used because they are cheaper and can be made in-house. As a result. – Titer less stable. + Simple handling. from VWR/MERCK) are commercially available to prevent this problem. and results in higher titration speed. favorably priced. methanol).g. Some manufacturers have slightly increased the pyridine content in the titrant to achieve a higher titration speed. which allow for fast and accurate Karl Fischer titrations. sulfur dioxide and 2-methoxyethanol. A titration speed two or three times as high can be achieved with the two-component reagent. increases their lifetime.

whereas the solvent contains sulfur dioxide.1 KF coulometry Coulometric KF determination of water is based on the standard reaction equation for the KF reaction.→ I2 + 2 e Iodine generation occurs at a generator electrode* (also called “generator cell”.2 Coulometric KF analysis 2.5 Karl Fischer reagents with ethanol Since ethanol is less toxic than methanol. * The terms "generator electrode" and "measuring electrode" mean an arrangement of two electrodes (anode and cathode) to form an electrolytic cell. diethanolamine and ethanol. a double pin platinum electrode. The titrant contains iodine and ethanol. The classical coulometric cell consists of two parts. the anode compartment and the cathode compartment. which is monitoring the potential of the sample solution by voltametric technique during coulometric titration. two-component. the iodine is generated electrochemically by anodic oxidation in the coulometric cell according to the following half-reaction: 2 I .2. however.1. imidazole. or “inner burette”) incorporated into the glass titration cell. 9 . Both parts are separated by a diaphragm. The generator is close to the measuring electrode*. These reagents also allow for titration of several ketones which form ketals considerably more slowly in ethanol than in methanol.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I In coulometry. 2. ethanol-based reagents were launched in 1998.

To calculate it. Note that methyl sulfonic acid. Depending on the application. can reach the cathode where it is reduced to a sulfide compound (obnoxious smell!). This consists of sulfur dioxide. 2 [RN]H+ + 2e. The catholyte is either a manufacturer-specific special reagent. Cathode reaction At the cathode. C.→ H2 + 2 RN Ammonium ions are then reduced with the formation of hydrogen and a free amine. 2. I2. the catholyte should be replaced once in two weeks. i. The value 96845 C/mol is known as the Faraday constant. I-. The cathode compartment contains the catholyte. is the quantity of charge that is transported by a current of 1 ampere in one second. imidazole and iodide salts. are oxidized to one molecule of iodine. the positive hydrogen ions are reduced to hydrogen. An ammonium salt is added to the catholyte in order to promote hydrogen production. Anode reaction At the anode.e.e. hexanol or ethylene glycol may be added. The negative iodide ions release electrons at the anode and form iodine. the KF electrolyte which is required for the oxidation in order to generate iodine by applying a current at the generating electrode. it is necessary to first recall the definition of 1 Coulomb: one coulomb. as chloroform. which subsequently reacts with water. 96485 C of current are needed.g. or the same reagent as used in the anode compartment.→ I2 → H2O 10 .METTLER TOLEDO Good Titration PracticeTM in KF Titration The anode compartment contains the anolyte. it is known that to produce one mole of a chemical substance that requires one electron. present in the anolyte compartment. This is the main product formed. Methanol or ethanol is used as solvent. 2 I. iodine reacts with water. iodine is generated from iodide by electrochemical oxidation. Subsequently. other solvents such e. This can cause the cathode to become black. C. used to generate iodine. releasing two electrons at the anode. To avoid this.2 Stoichiometry of the coulometric KF rection The amount of water titrated by coulometric technique is determined by the amount of electrical current given in Coulomb. the reagent that enables completion of the whole electrochemical reaction: the oxidation reaction in the anolyte compartment is completed by a reduction reaction in the catholyte compartment. octanol. 1C=1A·1s On the other hand. CH3SO3H. In Karl Fischer reaction two iodide ions.2. i.

the conductivity of the anolyte is influenced by the samples and additional solvents (chloroform. Since current and time can be accurately measured. As a consequence. etc. The maximum pulse height depends on the following factors: conductivity of the anolyte voltage at the generator electrode surface of the generator electrode The voltage at the generator electrode and the surface of the electrode depend on the type of coulometer.METTLER TOLEDO Good Titration PracticeTM in KF Titration Therefore. At very low conductivities (i. 2. coulometry is designated as absolute method. The main advantages compared to cells with diaphragms are: no contamination or blockage of the diaphragm easier cleaning lower drift 11 . the coulometer operates with current pulses of 400 mA. In addition.2.015 g/mol. For this reason. Since the molar mass of water is 18. 200 and 100 mA. less than 3–4 μS/cm). 300.2. For an electrochemically optimized Karl Fischer cell. hexanol.).4 Generator electrode without diaphragm with diaphragm without diaphragm The first commercially available diaphragmless cell for KF coulometry was introduced in 1989. it is strongly recommended that the coulometer is regularly checked by measuring a certified water standard. 2. The rate of iodine generation is adjusted by varying the pulse duration and frequency and the pulse height (in mA). this calculation can be expressed as follows: 1 mg of water corresponds to a consumption of 10.3 Iodine generation Iodine is generated by means of current pulses of 400. This gives an iodine generation rate which corresponds to a maximum of 2240 μg water/min.712 C electrical current. no standardization of the coulometric KF reagents is necessary. With standard conductivity values. the maximum possible current applied by the instrument is 100 mA.e. Nevertheless. it is used as a reference method for the determination of water content. the current conversion efficiency for iodine production is assumed to be 100%. 2 x 96485 C/mol is required for 1 mole of water.

METTLER TOLEDO Good Titration PracticeTM in KF Titration Originally..phenols (most) esters . etc. Nevertheless. lower than 50 μg water/sample).edible oils petroleum oils A cell with diaphragm is required for: samples with a very low water content (< 50 μg water/sample) very accurate determinations nitro compounds unsaturated hydrocarbons. In addition. the generator cell was first built with a porous ceramic frit (diaphragm) separating the inner cathode compartment from the anode compartment. This effect is further enhanced by the small dimensions of the cathode. To avoid this concurring reaction. the cathode is a small-size pin). R-NO2 + 3 H2 → R-NH2 + 2 H2O Besides this. a different geometry is used for the generating cell without diaphragm.5 Limitations for the use of the cell without diaphragm The cell without diaphragm is not suitable for samples that are easily reduced. a relatively high stirrer speed allows for more rapid distribution of the generated iodine molecules.g.acetamides etheric oils and essences . The latter can thus react more efficiently with water. However. may also be reduced at the cathode by the formation of water. The cathode is smaller and made in such a way that iodine cannot reach the cathode (i.chlorinated hydrocarbons alcohols . this makes it almost impossible for iodine to reach the cathode and be reduced to iodide. This is a very good reducing agent. The purpose is to prevent that iodine molecules generated at the anode are immediately reduced to iodide ions at the cathode instead of reacting with water. Note that hydrogen gas generated at the cathode is forming gas bubbles around its surface. especially for nitro compounds such as nitrobenzene.ethers ketones (with special reagent) .2. In practice. The diaphragmless cell is ideal for the determination of the water content of the following compounds: hydrocarbons . other easily reducible substances such as unsaturated fatty acids. 2. the relative error due to this effect can be minimized by using a larger amount of sample. Nascent hydrogen is formed at the cathode. for measurement of samples having a very low water content (e. 12 . it is still possible for a very small amount of iodine to reach the cathode. and for very accurate determinations. especially when easily reducible. Thus.e. the cell with diaphragm may yield more precise results.

the water content. and hence.1. there will be free iodine in the titration solution.the reaction rate of the Karl Fischer reaction . Ideally. 3. Free iodine causes ionic conduction and the voltage needs to be reduced to keep the polarization current constant.the termination of the analysis. the titration is terminated. The control of the titration is only possible if the end point is indicated. .the addition speed or generation rate of iodine . constant AC current – the polarization current "Ipol" – is applied to a double pin platinum electrode. iodine should be added or generated as quickly as possible. A small.the control algorithm and its parameters. . • • • As soon as all the water has reacted with iodine.1 Principle of bipotentiometric indication A bipotentiometric indication is used for the volumetric Karl Fischer titration as well as for the coulometric analysis (in electrochemical terminology this is also called "2-electrode potentiometry").METTLER TOLEDO Good Titration PracticeTM in KF Titration 3 Titration control and end point determination The addition or generation of iodine must be controlled. The resulting titration speed depends on the following factors: . • • As long as the added iodine reacts with the water. A high voltage is necessary to maintain the specified polarization current at the electrode. Only then can the titrant consumption or the generated iodine amount be determined with the desired accuracy. and the addition or production stopped exactly at the end point. 13 .the stirring speed and mixing of the sample solution. When the voltage drops below a defined value. there is no free iodine in the titration/anolyte solution. .1 Indication 3.the viscosity of the solution and its temperature.

400 mV to 650 mV is necessary to maintain the set polarization current at the double pin electrode. where they donate the electrons and form an iodine molecule. This leads to a termination of "ionic conduction" and the measurement signal becomes unstable. no iodine reaches the negatively charged platinum pin.e.e. I2. free iodine is present in the titration/anolyte solution. Iodide ions. Above all. then releases the electron again at the positively charged platinum pin and is again oxidized to iodine. If mixing is poor.(to a lesser extent) the type of electrode (i. this value depends on the polarization current. Ionic conduction Iodine takes up an electron at the negatively charged platinum pin of the indicator electrode and is thereby reduced to iodide (I-). At the end of the titration: As soon as all the water in the sample has reacted with the iodine. The two negatively charged iodide ions are attracted by the positively charged platinum pin. This free iodine gives rise to "ionic conduction". there is no free iodine in the titration/anolyte solution.the solvent or anolyte used in the instrument.METTLER TOLEDO Good Titration PracticeTM in KF Titration • The ionic conduction takes the following course: an iodine molecule is attracted by the negatively charged platinum pin. again. which are present in excess in the titration solution. Thorough mixing of the titration/anolyte solution is necessary in order to achieve constant "ionic conduction". A voltage of ca. It then acquires two electrons and turns into iodide ions (2 I–). Ipol . i.1. . The iodine is present only at low concentration. • • At the beginning and during the titration: As long as the iodine generated reacts with the water. the titration end point is reached if the potential at the polarized platinum double pin electrode drops below a specific predefined value.the polarization current.2 End point and polarization current The Karl Fischer titration is terminated when an excess of iodine is detected in the titration cell. The end point value mainly depends on . Now a low voltage of 50 mV to 100 mV is required to keep the polarization current constant. 3. geometry and dimensions of the metal parts) . This drop in voltage is used to indicate the end of the titration. respectively. 14 .

pin length: 3 . The layer is formed during the first ten titrations. and increases the sensor resistance. i. the following end points have been defined for methanolic one-component and two-component KF reagents using a V20/V30 volumetric KF titrator or T70/T90 Excellence titrator (double pin platinum electrode. the lower the pressure needed to transport the desired amount of water through the pipe (= smaller pressure difference). with longer pins. the polarization current should be set as low as possible. on the other hand. and increases the risk of over titration. In general the larger the platinum surface the smaller the current density. its surface can easily bond suitable chemical compounds.METTLER TOLEDO Good Titration PracticeTM in KF Titration For the volumetric KF titration. exhibit a smaller potential jump. e. However.g. a layer is formed on the surface of the platinum pin sensor. Sensors with a large platinum surface. pin length: 3 to 4 mm. On the other hand. With used sensors. Which polarization current should be used? A higher polarization current requires a larger iodine excess (indicated by a pronounced yellow coloration of the titration cell solution) to achieve ionic conduction for the determination of the end point. This makes it more difficult to stop the titration at the right moment. iodine excess should be as low as possible to get accurate results.e. pin diameter: 1 mm): AC Polarization current / µA 24 Endpoint / mV 100 For the coulometric KF analysis. a lower polarization current gives a smaller and steeper potential jump at the end of the titration. 15 . The larger the diameter of the pipe. Sensors with short platinum pins (< 3 mm). With use. i.e. and subsequently it remains constant.4 mm. The condition of the sensor has an influence on the potential jump Platinum is a strongly adsorbing metal. just after the equivalence point. a double ring or plates instead of rings. the following values have been obtained with a C20/C30 KF Coulometer (double pin platinum sensor. Influence of the sensor The potential jump at the end of the titration is also influenced by the geometry (surface and design) of the platinum sensing material of the sensor. The current density can be compared to a water pipe where a specific water has to flow. pin diameter: 1 mm): AC Polarization current / µA 5 Endpoint / mV 100 The same end point values can be used for ethanol based KF coulometric reagents. exhibit a larger potential jump and also a higher end point. this leads to a larger potential jump compared to a cleaned or a new sensor (without layer). As a consequence.

point of titrant addition (volumetric KF titration). which gives a high reaction rate. Example (V20/V30/T70/T90): One-component reagent Two-component reagent 2-3 min with a titrant consumption of 2.2 Reaction rate The reaction rate of the Karl Fischer titration depends on: .and on the iodine concentration.the sulfur dioxide concentration.0 mL In the coulometric KF analysis. the water content is high.5 . This results in a reaction rate up to 2 times faster for the two component reagent than for the one component reagent. stirring speed. At the beginning. the pH value of the solution has a strong influence on the rate and in particular on the stoichiometry of the Karl Fischer reaction. the water concentration is lower. In the volumetric KF titration. Stirring speed The optimum stirring speed is obtained when a distinct vortex is visible. If 16 . and the reaction rate also decreases: iodine must be generated or added more slowly because a small water amount is still present.2 min with a titrant consumption of 2.0 mL 1. If the speed is too slow. and overtitration may occur. Mixing is influenced by the 1. [SO2] . Karl Fischer titrations with the two component reagent are thus significantly faster than with the one component reagent. a large excess of sulfur dioxide is present in the solvent.the water concentration. [I2] . 2. [H2O] . On the other hand. the titration may also be too slow. with the twocomponent reagents. irregular.d[I2] / dt = k · [I2] · [SO2] · [H2O] In addition. shape of the vessel (volumetric KF titration). Iodine generation or addition can proceed rapidly because iodine immediately reacts with water. As a consequence. 3. Iodine generation or addition is usually the rate determining factor. 3.3 Stirring speed and dispersion of the volumetric KF titrant Good mixing is essential for fast and accurate KF titrations. lower reaction rates are achieved with anolyte solutions that have been used for a long time. Towards the end of the titration. note that sulfur dioxide is added only in slight excess with the iodine titrant solution when using one component titrant.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. sulfur dioxide is present in large excess in the anolyte. It is consumed with each additional measured sample leading to a decreasing dioxide concentration.

turbulence is not achieved and the mixing effectiveness is lower. but rather along the base directly towards the sensor. the stirring speed is too fast. leading to slower addition and longer titration time. Iodine would not be distributed upwards. Furthermore. Point of titrant addition The titrant should be added where the turbulence is the greatest to ensure efficient mixing. This is essential for a fast reaction rate and for short titration times. Vessel shape The conical shape of the beaker and the short stirring bar lead to turbulence at the point of titrant addition that effectively disperses the titrant. Otherwise the sensor may directly detect added iodine. Bubbles falsify the measured values. 17 . If a longer stirring bar is used. the point of addition should be sufficiently far away from the sensor to allow for sufficient time for reaction.METTLER TOLEDO Good Titration PracticeTM in KF Titration bubbles form into the solution.

The dynamic behaviour of the control can be influenced by a variation of the control band.4 Control parameters in the volumetric KF titration Several parameters can be defined in the titration method in order to optimize the method for the samples and the reagents. The following drawing reveals a schematical illustration of the control band: 18 .4. The recommended standard values are listed in the following table: Recommended standard values Sensor Ipol [µA] Stirrer speed [%] End point [mV] Control band [mV] Dosing rate (min) [µL/min] Dosing rate (max) [mL/min] Start Driftstop relative [µg/min] 1-Comp titrant 24 35 100 400 80 5 normal 15 2-Comp titrant 24 35 100 400 100 3 normal 15 3. Cautious The volumetric KF methods of the V20/V30 as well as T70 and T90 use KF titrant specific titration control parameters. An overview of the control parameters is given as follows: Volumetric KF Titration End point Control band Dosing rate (max) Dosing rate (min) Start: Normal.1 The Control Band The control band is a modifiable control parameter for both types of KF reagents.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3.

the titration starts with a slower acceleration (ramp up) than in the normal mode. With large amounts of water. 19 . at higher water contents. The closer the potential to the end point. i.The dynamics of the control can be influenced in the following way: Increase of the control band Aggressive control Smooth control Two different controls are used for 1-Comp and 2-Comp titrants. the slower is the titrant addition. 3.METTLER TOLEDO Good Titration PracticeTM in KF Titration The titrant addition is calculated on one hand by using the distance of the actual potential from the end point and on the other by using dE/dt. the control reacts more sensitively to potential changes. The 2-Comp titrant control reacts more sensitively to a potential drop than the 1-Comp titrant control. Burette size [mL] 1 5 10 20 Maximum dosing rate [mL/min] 3 15 30 60 Remark: Since the maximum dosing rate of a 1 mL burette is lower than the standard parameter 5 mL/min in the case of a 1-Comp titrant. In this case you can activate the Start: Cautious parameter. the titration starts so quickly that overtitration may occur. 3. 2. In particular. if the polarization current changes.g. The following points represent possible contributing factors: contaminated or old sensors.. if the control band width is decreased. sensors with very short platinum pins (< 3 mm). 3. The end point for a specific polarization current is influenced by the sensor and the solvent. longer titration times and poorer repeatability are resulting by selecting a higher end point potential value. This is more suited for small water amounts. Dosing rate (max) = 2 mL/min. Recommendations 1. You can also set the maximum dosing rate to a lower value for small amounts of water if you wish the titration to progress more cautiously.4.2 The minimum and maximum dosing rate Both rates limit the dosing speed of the titrant to an upper or lower level. You should select Start: Cautious for one and two component reagents if the amount of water in the sample is less than 500 µg. In both cases (normal and cautious mode) the maximum dosing rate will be reached at the end of the ramping up.4. the end point must be adjusted. The maximum dosing rate is dependent on the actual burette size.4. Thus.e. In the cautious mode. the titration will take too long. the titrator automatically issues a warning. which leads to a stronger reduction of the dosing speed.3 The Cautious start If the water content is very low.4 Polarization current and end point Each end point is valid for a specific polarization current. however. e.

the control band shall be decreased to 100 mV and the maximum dosing rate decreased to about 50%. • If Chloroform or Xylene is added in order to dissolve oil samples.4. Auxiliary reagents • If formamide is added to the solvent. This measure allows the system to cope with the reduced conductivity. this results in an illdefined titration end point. Therefore the potential jump at the end of the titration is smaller compared to conventional reagents. the titration can be accelarated by reduction of the control band to 300 mV. used as solvent. 20 . the titration curve is more or less flat towards the end. If 2-comp ethanolic reagents are used. the overall ionic conductivity is decreased. 2-propanol.g.METTLER TOLEDO Good Titration PracticeTM in KF Titration - long alkyl chain alcohols. instead of methanol or ethanol. Therefore it is recommended to decrease the polarization current to about 15 μA. which will lead to long titration times and to low precision. This results in a lower voltage required to maintain the polarization current. the maximum dosing rate can be set higher for certain reagents: 4 mL/min for Riedel de Haen 2-Comp 5. setting up of the titrant as 1-comp KF titrant yields shorter titration times. the overall ionic conductivity is increased. • • If 1-Comp titrants are used with Ethanol (e. the system reacts slowly in the case of ethanol based reagents. Ethanol-based reagents • Compared to the methanol-based reagents. table) work fine. Composolver E) the standard 1-Comp parameters (cf. 3. • If 1-comp titrants are used. In order to achieve a good repeatability. up to 8 mL/min for most 2-Comp 2 titrants. If one-component reagents are used. • If 2-comp titrants are used. the sensor current shall be reduced to 15 μA. e.g.5 Application tips Methanol based reagents • The standard parameters listed in the table above are ideal for the titration with methanol-based reagents. The consequences of choosing a too low end point value are illustrated in the figures above: On the right side.

Fix (400. If the titration takes too long.g. 3. In the case of 2-comp reagents over titration can be prevented by reduction of the maximum dosing rate.4. However the control band shall not exceed the start potential. 2-methoxyethanol. the 1-Comp control is suitable for systems that show an oscillating potential behaviour. This control is also recommended for 2Comp systems that show a noisy signal at the beginning of the titration. The minimum dosing rate shall be used to fine tune the final phase of the titration. 2. which is the case in 1-Comp systems.5 Control paramaters in the coulometric KF Analysis An overview of the relevant control parameters is given as follows: End point Control band Rate: Normal. ->Use the 1-Comp control Smooth system behaviour ->Use the 2-Comp control t 3. E E t Oscillating system behaviour. 300. where the methanol has been replaced by e. an increase of the control band is recommended. Cautious Generator current: Automatic. In most cases 300 – 400 mV are well-suited. 200.METTLER TOLEDO Good Titration PracticeTM in KF Titration KF reagents for ketones • An end point value of 150 mV for both one-component and two-component reagents is recommended when using special KF reagents for aldehydes and ketones. In general. which is the case in some ethanolic reagents. 3.6 General recommendations 1. 100 mA) 21 . The most straight forward influence on the control behaviour is achieved by a variation of the maximum dosing rate. There is no need to accurately adjust the control band to the actual start potential. Furthermore it is recommended to reduce the polarization current to a value of 15 μA.

and improved KF titration stands (i. This parameter shortens the titration time and leads to repeatable results.g. minimum titration time 22 . less than 50-100 μg water per sample). the pulse height can be automatically changed by the system if in the titration method the control parameter “Generator current” is set to “Automatic”. Normal: This iodine generation mode is generally used for all water content determinations. it has been possible to reduce the delay time to 5 to 10 seconds due to the introduction of • • • new. Later on. iodine is generated by means of current pulses of 400. relative drift stop. More specifically. Five termination parameters can be defined in the titration method: delay time. The closer the measured potential value from the predefined end point is.25 µL for a 5 mL burette). 300.METTLER TOLEDO Good Titration PracticeTM in KF Titration The iodine generation rate in the C20/C30 Coulometric Compact Karl Fischer Instruments depends on the distance from the end point. The fixed setting is used for solutions that exhibit a difficult characteristic with respect to conductivity. i. The coulometer provides two different modes for iodine generation under the control parameter “Rate”: 1. Cautious: Suitable for samples of low water content (e.Fix). Since the first developed KF reagents reacted slowly.e. absolute drift stop.e. 2. i.e.. In particular.6 Termination parameters for both coulometric and volumetric KF titration The KF titration can be terminated using various parameters. pyridine-free reagents with a faster reaction rate. 3. a delayed switch-off time of 10 to 20 seconds was set at the end point. the slope of the iodine generation is steeper and the rate is increased based on the measured potential value. 200 and 100 mA. the iodine generation is higher than in the cautious mode. high resolution burettes (0. as soon as the was potential value was lower than the set end point during the defined delay time. tightly sealed stand). Variation of pulse length (time). i. In addition. the slower is the generation of iodine. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. the online determination of the drift during analysis has enabled a so-called "drift stop" to be used as a termination parameter. The iodine generation starts slowly. pulse frequency and pulse height (mA) are used as variables by the instruments. or it can be set to a specific value (“Generator current” . then the titration was stopped. maximum titration time. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA.e. the slope of the iodine generation rate is flat at the beginning of the titration. Initially.

m the drift before titration) and the relative drift. the titration is terminated and the result is printed. Disadvantage: The value optimized to the initial drift. 23 . Thus. otherwise the termination criterion will never be reached. Typical delay time: 5 . otherwise the termination criterion is never satisfied. the absolute drift stop value must be greater than the initial drift. After the defined time has elapsed.METTLER TOLEDO Good Titration PracticeTM in KF Titration Delay time The titration is terminated when the potential remains below the end point for a defined time (e. • Advantage: This parameter ensures a high repeatability of the results. Typical absolute drift stop value: 3 µg/min (coulometric). . especially if working with the KF sample oven. Disadvantage: The minimum rate must be adapted to the initial drift and the titrant concentration.15 seconds (Coulometric/Volumetric) • • Advantage: well-known method. The smallest increment must be sufficiently large to compensate the drift. Absolute drift stop Termination occurs as soon as the actual drift drops below the predefined absolute drift value.Maximum titration time The titration is terminated after the defined time. 5-15 μg/min (volumetric) • Advantage: independent on the initial drift. titrant concentration (volumetric) and side reactions. 10 µg/min (volumetric) • Advantage: Independent on the titrant concentration.e.g. easy to understand (volumetric). has to be t/s • Relative drift stop The titration is terminated as soon as the actual drift drops below the sum of the initial drift (i. 15 s) following the addition or generation of iodine. Typical value for the relative drift stop = 2-5 μg/min (coulometric).

but involves a risk that the titration will be terminated a bit too early. • Advantage: This parameter ensures a high repeatability of the results. the following values are recommended for volumetric KF titration: One-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. 3. soluble samples You should normally choose the relative drift stop as a termination parameter. If the water content is relatively high. i. The vaporization of water is also irregular in the final stages. This is particularly critical in connection with the "slower" reagents for ketones and aldehydes. The final traces are only extracted very slowly.6. This termination parameter is also well-suited when the internal extraction is needed to determine the water content in insoluble sample: The water contained in insoluble samples is extracted during the titration. this is the simplest and most universal parameter to use. This parameter is independent of the the initial drift (coulometric. possibly resulting in poorer repeatability and lower water contents. you can terminate the titration at a higher drift (relative drift stop = 40 to 70 µg/min).e. A relative drift stop of 20 to 40 µg/min shortens the titration time without affecting the repeatability. The value of the relative drift stop influences the repeatability and the titration time: • • Drift stop (low value) → better repeatability poorer repeatability → → long titration time short titration time Drift stop (high value) → In particular. the drift at the end is often greater than the initial drift. so 24 . A relative drift stop of 20 to 30 µg/min shortens the titration time.. Maximum titration time for determinations with the KF drying oven When using the drying oven.1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration The following termination criteria are most commonly used for water determination by Karl Fischer titration: Relative drift stop for trouble-free. volumetric). The reason for this is either a very slow release of the last traces of water or a slow thermal decomposition of the sample. It is recommended to be used for substances that release water slowly. Use the drift/time curve to determine this value.METTLER TOLEDO Good Titration PracticeTM in KF Titration .Minimum titration time Titration is not to be terminated before this time in [s] is reached (exception: the maximum volume has been reached). and the titrant concentration (volumetric). Thus. Two-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. you can ignore these traces.

If the drift stop value is not reached. The higher drift is therefore influenced to a large extent by the sample. This is the case with samples that only release the final traces of water very slowly or that produce side reactions. A combination of the relative drift stop and the maximum titration time has proved effective for such samples.METTLER TOLEDO Good Titration PracticeTM in KF Titration that the repeatability of the titration termination using the drift stop parameter is poor. (Set the minimum titration time equal maximum titration time). 25 . It gives you the best accuracy and repeatability of results. Note: To obtain accurate and reliable results you should only work with the coulometer when the drift is lower than 10 µg/min. the titration is terminated at the latest after the defined maximum time. If the drift is greater than 10 µg/min. you should take measures to reduce the drift. Relative drift stop/maximum titration time for problematic samples Some samples lead to a high drift value at the end of the titration. the maximum titration time has proven to be best termination criterion in practice. Therefore.

METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. Do not shake too vigorously to avoid solvent gets on the cover of the vessel. The Karl Fischer titrator should never be installed close to a ventilator of the air conditioning system! 4. The drying capacity of the desiccant is limited and it depends on the humidity and can be exhausted after 2 . the residual moisture dissolves more rapidly into the anolyte (solvent).e. since cold air cannot absorb as much moisture. where the relative humidity can achieve values of more than 80%. Condition the titration cell before use. The factors include: • • • • the atmospheric humidity the working medium the pH of the sample the side reactions between the sample and the Karl Fischer reagent 4. The air within the titration vessel also contains moisture. the greater is its influence on the results of the Karl Fischer titration. This problem is particularly relevant in tropical climates or in coastal regions. When you assemble the titration stand for the first time. the higher the atmospheric humidity in the laboratory. In this way. This can take 1 . the titrant and the titration stand. However. The drift. Briefly. the relative humidity increases. The total moisture can be titrated more quickly by gently moving the vessel from side to side so that solvent swirls up the side of the vessel to pick up moisture adsorbed on the glass walls. Silica gel can be regenerated over night at 150 °C. i. The desiccant absorbs the moisture and protects the titration cell against the ingress of moisture. however. After the anolyte (coulometer) or the solvent (volumeter) has been added.1 The influence of atmospheric humidity (drift determination) Atmospheric humidity represents the most relevant source of error in Karl Fischer titration. there will be moisture on the glass surface of the titration cell and the inserts. remains high because the moisture present on the glass walls and the air in the titration cell diffuse only slowly into the anolyte (solvent).1 Titration stand The titration stand must be sealed as tightly as possible against atmospheric moisture. The following rules should be observed: • • Close all openings in the titration stand. Moisture can enter the sample.3 hours. The assumption that air-conditioned rooms have a lower atmospheric humidity is often not true: the majority of air-conditioning systems simply cool the air. The air-conditioning system should therefore be equipped with a moisture condenser.1. whereas molecular sieves require temperatures up to 300 °C. • Protect the titration cell with a desiccant (3 Å molecular sieve and silica gel). it is titrated to dryness during pretitration. The Karl Fischer titration Various factors must be taken into account with Karl Fischer titration to obtain correct results. until it is absolutely free of water.4 weeks (indicated by a colour change of the indicator of the silica gel). 26 .

the KF titrator continuously titrates the water that diffuses into the cell. it is necessary to quantify the amount of water entering the titration cell during titration.2 The drift No titration stand is completely water tight.1. At the start of a sample titration. if it is defined as the parameter “Source for drift: Online” in method function “Titration stand (KF stand)”. the drift value should therefore be as low as possible and stable before the start of a titration! 27 . the last measured drift value is automatically stored. and its value is displayed on the screen. or a fixed value can be defined into the titration method (“Fix value”). t. and is given in μg water/minute. Therefore it must be taken into account when calculating the water content. traces of water will always find a way into the titration cell. or it can be entered by the user (“Request”): Source for Drift Online Determination Fix value Request Explanation Last measured value of standby The drift is determined and stored as raw result DRIFT A fixed value is defined into method The value can be entered immediately after starting sample titration The drift value is subsequently used in the calculation of the result in order to compensate for the moisture that entered the titration cell according to the following formula: Sample result = Total amount of water determined . On the other hand. Therefore.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. In the standby titration. For accurate results. it is also possible to use the value of a previously performed drift determination (“Determination”). this water amount is also titrated during analysis. This is achieved by titration of the dry solvent for a defined time (drift determination). On the other hand. In this respect. the drift indicates the quantity of water that enters the titration stand over a defined period.(drift * titration time).

a flow occurs from the cathode compartment to the anode compartment. some anolyte solutions contain an excess of iodide and the solution has a brown colour. If this is not the case.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4.The generator electrode should dip approx. If the level of the catholyte is the same or higher.Take approx. 2. 100 mL anolyte. 2. you must add some methanol or sample so that the color changes to yellow.Make sure that the level of the anolyte is approx. the level of the anolyte drops due to evaporation. 5 mL from the bottle with a syringe and inject it into the generator electrode or empty an ampoule of catholyte into the generator electrode. Normally this brown coloration disappears on filling the titration cell because the iodine excess is consumed. In this case. .The difference in level between the anolyte and catholyte is maintained as long as the stirrer is in operation.5 cm into the electrolyte solution. . .2 Working with the coulometric KF instruments 4. However. By ensuring that the level of the anolyte is higher than the one of the catholyte.Pour approx. when the drying oven is used. Higher anolyte level → low drift Lower anolyte level → drift is high .1 Filling the coulometric cell • Cell with generator electrode with diaphragm . .Then fill the anode compartment with approx. 100 mL electrolyte solution (anolyte) into the titration cell. which leads to a higher drift. the moisture enters the diaphragm and is slowly released into the anode compartment. 28 .2. The catholyte always contains traces of water. the level of the anolyte increases.First transfer 5 mL catholyte to the cathode compartment. Note: In production. 3 . As soon as the stirrer is switched off. This can be avoided as it follows: 1.5 mm higher than that of the catholyte. • Titration cell with diaphragmless generator electrode . the levels slowly become the same. The catholyte can be dehydrated with a few drops of a volumetric KF one component titrant. . the anolyte should be topped up from time to time with anhydrous methanol.When a sample is injected into the anode compartment.

If an emulsion forms in the anode compartment. The Solvent Manager is located on top of the waste bottle and includes strong air pump (diaphragm pump) and an electromagnetic valve. This can lead to wrong results.Catholyte solutions (5 mL): after 200 mg water. If the drift is too high. it is common use to replace both the anolyte and catholyte at the same time If after adding samples. This can happen if large amounts of samples of low conductivity are titrated. . e. the drift slowly increases. After being used for two weeks.2.g. The higher the level in the anode compartment. the dissolving capacity of the anolyte (coulometric KF) is exhausted and an emulsion is formed.2.3 Secure draining and filling of the titration cell: SOLVENT MANAGER The easiest and secure way of draining and filling the coulometric titration cell is performed with the external KF liquid handling device Solvent Manger. With poorly soluble samples. If the conductivity of the anolyte drops to a very low value. The working principle of the Solvent Manager is illustrated in the following schematical illustrations: 29 . below 10 μS. In practice. Any contact with the reagent is avoided during draining and refilling of the titration cell.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. the worse the stirring efficiency will be. • • • • • 4. . It is fully controlled by the titrator. and the risk of over titration increases.2 When do you have to replace the electrolyte? The electrolyte must be replaced in the following situations: • If the capacity of the electrolyte is exceeded. In the cathode compartment sulfides and mercaptans are formed that lead to an obnoxious smell and a higher drift. The capacity is monitored by the coulometers (see operating instructions).Anolyte solutions (100 mL): after 1000 mg water. the level of the solvent or the anolyte exceeds the 150 mL mark. when using a generator electrode with diaphragm. A level sensor in the waste bottle prevents from overflow. If an electrolyte is used for a long period without replacement.

Step 2: The Anolyte is drained into the waste bottle by applying vacuum.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 1a: Put the draining and reagent refill tube into the coulometric titration cell. Step 1b: Start the reagent replacement either from the manual function ‘Replace reagent’ or from a predefined Shortcut on the Home screen of the Touchscreen. 30 .

Step 4: After a predefined time or by manual interaction the pressure within the solvent/anolyte bottle is relieved by switching the magnetic valce into the initial position. The Solvent Manager is part of the standard delivery of the C20 and C30 Compact coulometric KF titrators. Depending on the type of the generator cell the following liquid handling actions can be performed: Diaphragmless generator cell: Replacement of the anolyte Generator cell with diaphragm: Replacement of the anolyte and draining of the catholyte 31 . An optional reagent exchange set consisting of tubes. In this configuration only draining of the titration cell is possible. drying tube and tube holder enables both draining and refilling.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 3: The pump direction is switched by activation of the magnetic valve and subsequently fresh solvent is pumped into the titration cell by applying over pressure of dry air.

Simple cleaning and drying of the generator electrode Method A: . The C30 provides a reagent monitoring routine which is called Reagent Control. The generator electrode with diaphragm must be cleaned periodically because contamination accumulates in the diaphragm over a longer period of time. .Afterwards dry the generator electrode at a maximum temperature of 50 °C in an oven or with a hot air dryer.Fill the generator electrode with anhydrous methanol. since it would cause a higher drift value. Moisture and contaminants are rinsed out of the diaphragm. . • Thorough cleaning of the generator electrode If the generator electrode and the diaphragm are strongly contaminated.Methanol flows through the diaphragm into the cathode compartment. It provides the following: Monitoring three reagent parameters Usable life in days Capacity in mg water Number of samples When due. then with anhydrous methanol and dry it as described above.2. which leads to a higher drift. • Cleaning the titration vessel Clean the titration vessel with water or a suitable solvent. the most effective cleaning agent is chromic acid. especially if dirty samples are analyzed. Drying is not necessary if you use it immediately. Afterwards dry the vessel at 100 °C in an oven or with a hot air drier. . • 32 . If immediate use is required rinsing with anhydrous methanol shall be applied. reagents can be replaced directly out of running method Choice of enforcing the user to replace it immediately or ask again later 4. The procedure is identical to that described above. Method B: .This procedure should be repeated at least once.Place the empty generator electrode in anhydrous methanol.METTLER TOLEDO Good Titration PracticeTM in KF Titration Note: The tubes for anolyte exchange are not left in the titration cell during titration. Methanol flows through the diaphragm and rinses out moisture and contaminants. Place the empty generator electrode in the chromic acid or fill the generator electrode with chromic acid and let it flow through. The contaminants can originate from samples or are side products that have been formed in the cathode compartment by reduction. Afterwards thoroughly rinse the generator electrode with water.4 Cleaning the coulometric KF titration cell The titration cell and both electrodes should be cleaned.

so that there is a sharp drop in concentration. 2. As already described. • Clean the platinum pin with a paper tissue. while the two-component titrant is rather stable). 4.1 How often should the concentration be determined? How often the concentration is determined depends on the choice of titrant.3. Based on the chemical stability of the titrant. the one-component titrant. This leads to a higher potential jump. which prevents a good indication. 2) Connect the S7 connection of the generator cell with the indication electrode. • With heavily contaminated electrodes. The Ohmic resistance of the electrode is increased. the tightness of the titrant bottle and the desired level of accuracy. the measuring electrode must be cleaned. We recommend to determine the titrant concentration daily. In countries where the temperature varies considerably during the course of the day and the lab is not air-conditioned. The layer should therefore not be removed by cleaning. it is better to determine the concentration every 2 to 4 hours. 4. 3) Stop the method when the cleaning is finished so that the polarization current at the indication electrode is stopped. In this case. a layer is formed on the platinum surface after the first few titrations.g. A significant change in temperature may occur: The Karl Fischer titrants consist of approximately 90% methanol or ethanol. The volumetric KF titrators enable monitoring of the usable life and life span of the titrant. a weekly titer determination would be sufficient (the concentration of the one-component titrant changes by 0. .5 mol/L sulfuric acid.if the titrant bottle is not tightly sealed. samples may be deposited on the surface of the electrode. The titrant is not chemically stable.3 Volumetric KF Titration: Titrant concentration The titrant concentration can change due to the following reasons: 1. Their volume increases considerably with temperature.if the desiccant on the titrant bottle is "used up". This also becomes noticeable through a dark coloration of the anolyte at the end point.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. e. 3. place the electrode in 0. the indicating electrode does not need cleaning. The titrant may absorb moisture from the atmosphere reducing its concentration (the anhydrous methanol in the titrant is very hygroscopic) .2. The tightness of the titration stand and the proper functioning of the burette and the end point indication are also checked at the same time as the concentration is determined. This is sufficient in most cases.01 mg/mL per week.5 Cleaning the measuring electrode Generally. repeatable results. A reminder can be set to warn the user at the start of every titration that the usable life is about to expire in the predefined time range (days). This test of the complete system by a titer determination is therefore an essential condition for accurate. In the global settings within the setup menu of 33 . and let an electrical current of about 400 mA flow across the platinum pins for 60 s by starting the KF titration: 1) Disconnect the S7 connection of the indication electrode. However.

5 mL with a 5 mL burette.08 g di-sodium tartrate dihydrate with the aid of a weighing boat. Note: 1. Rinse the burette 2 times into a waste bottle before you determine the concentration. it contains 15. i.e.3. Either the user is simply warned or the usage of the expired titrant is blocked. 4. is the primary standard for Karl Fischer titration since it is stable and non-hygroscopic.3 to 2.: .and at the same temperature. Under normal conditions.METTLER TOLEDO Good Titration PracticeTM in KF Titration the titrator actions can be defined that will be applied if the usable life or life span is actually exceeded. - 34 . The plastic tubing is not absolutely water vapor-tight. Determine the concentration under the same conditions as for sample analysis. Mix for 3 minutes to achieve complete dissolution before you start the titration. This sample size yields an optimum titrant consumption of 1. Make sure that nothing adheres to the beaker wall or to the electrode. which prevents the execution of further titrations.2 Concentration determination with di-sodium tartrate dihydrate General Di-sodium tartrate dihydrate.04 and 0. Add it into the titration vessel.08 g/mol). i. Since it slowly dissolves in methanol.66% of water. thus the titrant concentration slightly but continuously decreases slightly when left to stand for a long time. 26-50 % of burette volume. .e. you should first grind it to a fine powder before using it or use special Di-sodium tartrate dehydrate for Karl Fischer Titration Procedure . 2.Use the optimized METTLER TOLEDO method M301 Weigh between 0. Na2C4H4O6•2H2O (M = 230.using the same titration stand with the same volume of solvent. Determine the weight by back weighing and enter it as sample size.

3 Concentration determination with Water Standard 10. "HYDRANAL®-Water Standard 10. You must perform the determination in pure methanol! Less soluble. mixing time 1 minute. Highly soluble. You cannot perform more than one determinations in 40 mL of ethanol (with 0. Slightly soluble. Thus. In Solvent*/chloroform mixture 1:1 or Solvent*/decanol mixture 1:1 In Solvent*/formamide mixture 1:1 In methanol In methanol/chloroform mixture 1:1 or methanol/decanol mixture 1:1 In methanol/formamide mixture 1:1 In solvent for aldehydes and ketones (one-component reagent) In ethanol *Solvent: solvent for the two-component reagent 4. mixing time 2 to 3 minutes. They are thus protected against the ingress of moisture and can be stored for up to five years.3. This content is confirmed by the test certificate enclosed with every package. 35 .e.05 g di-sodium tartrate). The water standards are supplied in glass ampoules. You can perform six determinations in 30 mL of Solvent* before you need to change it. mixing time 2 to 3 minutes. You must perform the determination in pure methanol! Highly soluble.0" from Sigma-Aldrich® with 10 mg water in 10 g standard. 30% too high.045 g di-sodium tartrate). Less soluble. Partially soluble.5 g of water standard 10. you should weigh in 1. mixing time 1 minute.0 mg/g General Water standards consist of a mixture of organic solvents containing a specific amount of water. You can only perform one determination in 50 mL of 1:1 mixture (with 0.0. e.g. The values that are obtained are approx. Partially soluble. too high titer). You must either change the solvent after every sample or use pure Solvent* for the determination. You can perform eight determinations in 40 mL of this mixture before you need to change the solvent. mixing time 5 minutes. Procedure To achieve an optimum consumption of 2 to 3 mL titrant with a concentration of 5 mg/mL.METTLER TOLEDO Good Titration PracticeTM in KF Titration Solubility of di-sodium tartrate dihydrate Di-sodium tartrate dihydrate must be completely dissolved (clear solution!) to obtain correct results.0 to 1. A cloudy solution will falsify the results (i. always take into account the limited solubility of di-sodium tartrate dihydrate in the most commonly used solvents for Karl Fischer titrations: In Solvent* Highly soluble.05 g di-sodium tartrate dihydrate). The values obtained are approximately 10% too high. mixing time 1 minute. You cannot perform more than three determinations in 40 mL of methanol (with 0.

Inject 1 to 1.0 mg/g water standard. Start the titration without any mixing time. Use the METTLER TOLEDO method M300 The water standard is highly soluble in all commonly used solvents for Karl Fischer titration and can therefore be used without restrictions. – – – 36 . Glass syringes are better. Enter 0. 6. To reduce the influence of the atmospheric moisture. 4. Procedure – – You should weigh between 10 and 20 µL of deionized water or water according to ISO 3696 to achieve a consumption of 2 to 4 mL titrant with a concentration of 5 mg/mL.3. 4. the whole content of the ampoule is completely drawn into the syringe. with a Hamilton microliter syringe). In an open ampoule the liquid standard is exposed to air moisture. 3. Open the ampoule shortly before the measurement in accordance with the enclosed instructions. Use a new ampoule for each new concentration determination. Inject exactly 10. A balance with a resolution of 0. it is strongly recommended determining the concentration either with di-sodium tartrate dihydrate.0 µL deionized water with a 10 µL syringe. Draw the whole content of the ampoule into the 10 mL syringe.5 mL at a time as an aliquot. The content of an ampoule is sufficient for 3 to 5 determinations. Start the titration without any mixing time.0 mg water/g for a titrant concentration of 2 or 1 mg/mL. or with a 10. the water content is increased and thus this will falsify the results. This is due to the very small amount of sample (10 to 20 µL) that has to be injected. a very good deal of practice and precise working is required to obtain repeatable. Thus. The sample should be weighed either using a balance with a resolution of 0.g.g. The error is minimized by rinsing and conditioning the syringe beforehand.1 mg does not satisfy the requirements for a repeatable titration. 5.4 Concentration determination with pure water General When using pure water to determine the concentration. You can use a water standard with 1. METTLER TOLEDO XP205 balance) or with a 10 or 20 µL precision syringe (e. Determine the weight by back weighing. 2.01 g as the sample size.01 mg (e.METTLER TOLEDO Good Titration PracticeTM in KF Titration – – – – – – Notes 1. accurate results. Rinse a 10 mL syringe with approximately 1 mL of water standard. Plastic syringes may introduce a small amount of moisture.

ethereal oils Petrochemical products: gasoline. dioxane. the sample must release water completely. It is possible to determine the titrant concentration with water in all the solvents commonly used for Karl Fischer titration. wipe off any drops that have adhered to the needle with two fingers (be careful if you use a paper towel. noodles. Solvent Methanol Max. salicylic acid Foods: honey. 2. transformer oil. corn. You should always observe the following points when determining the concentration with a 10 µL syringe: Precondition the 10 µL syringe for approximately one hour by filling it with water. to avoid touching the glass part. Insert the syringe through the 1 mm hole of the three-hole adapter. yogurt.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. Only freely available water undergoes reaction with the Karl Fischer reagent. lay it down on the adapter and empty it completely. Always use a syringe with a long metal shaft.5 The solvent To determine the water content in a sample. diesel oil. massage oil. Adjust the plunger to exactly 10. hydraulic oil. caramel. potato chips Chloroform Decanol Octanol Hexanol Dodecanol Toluene Formamide 70% 50% 50% 50% (30%) 37 . if it is absorbent. You can get rid of any bubbles in the syringe by expelling the water rapidly. emulsions Petrochemical products: crude oil. beverages Cosmetics: soaps. After setting the volume. Do not warm the syringe. You can use mixture of solvents to achieve complete dissolution. Hold the syringe at right angles directly in front of your eyes to read off the value. ester Organic products: urea.0 µL. Always add each sample in exactly the same way. the largest part of the solvent mixture must always be an alcohol (most preferably methanol) to ensure that the Karl Fischer reaction is strictly stoichiometric. kerosene Pharmaceutical products: ointments. creams. alcohols. tar products. it may draw water out of the needle!). amount 100% Samples Solvents: toluene. fat Oils: edible oil. However. All the screws in the syringe must be tightened securely. fatty creams Waxes.3. jelly bears Starch products: flour. - 4. suppositories Sugar products: jelly.

too low water content.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. buffering agents are first added to the solvent to ensure that the titration is quick and without side reactions: .6 Dissolving capacity of the solvent The dissolving or extraction capacity of the solvent is a crucial factor in Karl Fischer titration.g. The solvent for the two-component reagent contains SO2. formamide effectively extracts water from starch products.salicylic or benzoic acid for basic samples. starch products will not dissolve in it. you must replace the solvent timely. The solvents that are used should contain as few water as possible (< 100 ppm). 38 . or by indicating the maximum number of samples to be titrated.imidazole is used for acidic samples. and . the titration of subsequent samples will then be very slow. Therefore. In this case. or the titration will take too long and titrant will be wasted. The Compact Line KF titrators are able to monitor the solvent capacity: the user can define when the solvent should be replaced by specifying the usable life. the water will no longer be completely released. it is necessary to replace the solvent timely. The extraction capacity can be improved by increasing the temperature (e. On the other hand. or the stoichiometry of the Karl Fischer reaction will change and the results will be wrong. i. If acidic or basic samples are titrated. 4. This will lead to incorrect results. Sugar is the only type of sample that dissolves in formamide. If exhausted. the amount of water in mg which has been titrated. The amount of formamide at 50 °C should not exceed 30%. Once again.3.e. 2. 3. 50°C). The titrator accumulates the total water amount continuously during titrations and reports "Solvent capacity exhausted" as soon as the specified value is exceeded. which may be completely expended if you titrate a large number of samples with high water content.

and thus air moisture can penetrate the plastic and absorbed by the sample.g. you should determine its water content as soon as possible. It floats on the surface or sinks to the bottom. such as butter. you must be extremely careful to exclude atmospheric moisture . 39 . The sample should be taken quickly to exclude. Use bottles with a septum stopper for liquids of very low water content. you will no longer be able to determine its true water content. 4. With liquid samples. i. In the case of non-polar solids.1 Taking the sample When taking samples for water determination. keep it in a tightly sealed bottle: Glass bottles are preferable to plastic bottles because plastic is not completely gastight. rinse the bottles two or three times with the sample beforehand.e. This can happen when a sample cools and the water solubility is decreased. The sample must therefore be taken very quickly and with a syringe or a spatula that is absolutely dry. the lower the amount of moisture. If you have to store the sample. Use a bottle with an optimum volume for the amount of sample: the smaller the gas space above the sample. In such cases. e. The sample must be representative. Liquids of this type must be thoroughly mixed (by shaking) before a sample is taken. it must contain the same average amount of water as the material as a whole. 5. you should take into account the following points: 1. the water is not uniformly dispersed. which cannot be mixed as thoroughly as liquids. If the water content of a sample changes during sampling due to moisture being absorbed or desorbed. 3. or at least minimize. oils. Heterogeneous water distribution in samples: In non-polar liquids. Substances with very low water content: Substances with a very low water content are frequently extremely hygroscopic. 5.2 Storing the sample After you have taken the sample. the solubility of water in the sample can be increased using a solubility promotion agent such as 2-propanol. Hygroscopic solids may exhibit higher water content on the surface than inside if they have absorbed atmospheric moisture during storage. the absorption or release of moisture.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5 Sampling 5. water may be separated from the sample if it is left to stand for a long time. the sample should be larger the more heterogeneous the distribution of the water. "An analysis cannot be better than the actual sample!" When sampling. 2. Use sample bottles with small openings to minimize the ingress of moisture. With liquid samples that do not dissolve water such as oils.the most common source of error.

05 mg water per sample with a titrant concentration of 1 mg/mL. sample size Amount of water [ppm] [g] [mg] 1 10 0. the accuracy is improved if larger sample amounts are used. the optimum amount of water is in the range from 0.01 10 8 0.5 to 17. As a rule of thumb.1 to 0. the accuracy increases with the amount of sample.4 500 2 1. For a more accurate determination of water traces (10 ppm to 1000 ppm) by volumetric KF ttiration.0 10000 = 1% 0.25 100 4 0. because the absorption of atmospheric moisture during sampling or sample addition becomes less important. For optimum accuracy with determinations in the range from 1 ppm to 1% water. because the absorption of air moisture during sampling and sample addition becomes less important.3 Amount of sample The amount of sample used depends on • • the expected water content.2 1. In general.1 1. This corresponds to 7.5 to 2 mg water per sample. and the required accuracy and precision. This corresponds to 0. If a high level of accuracy is required.0 1000 1 1. approx. Water content determinations below 1000 ppm are not required to be quite as accurate: a relative standard deviation srel of 1 to 5% is generally considered as acceptable for such values. Under optimum measurement conditions.0 For volumetric titrations. the amount of sample should require a titrant consumption between 30 and 70% of the nominal burette volume.08 50 5 0.05 mL is thus still acceptable when using a 5 mL burette. the optimum amount of water is approximately 10 mg per sample. it is recommended to use the minimum sample size given in the following table: Water content Min.5 mg water per sample for a 5 mL burette with a titrant concentration of 5 mg/mL. For coulometric analyses.0 5000 0.1 mg water per sample.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5. A titrant consumption of 0.1 to 0. sample size [ppm] [g] 10 8 50 7 100 5 200 4 500 3 1000 2 40 . 10-50 μg water can be detected if the demand for repeatability is not too high. Repeatable results can be obtained even with 0. and the following minimum sample sizes should be used: Water content Min. a KF titrant with a lower concentration (1 or 2 mg/mL) has to be used.

Procedure: • • • Note: Start from the optimum point (10 mg for volumetric KF. 1 mg for coulometric KF) or the recommended range The optimum point is connected by a straight line to the expected water content. The intersection point of this line with the "Amount of sample" scale represents the recommended amount of sample to be used. Logarithmic scale! 41 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Determination of the amount of sample for a water content in the range from 1000 ppm to 100% Principle: The recommended sample size can be determined as a function of the expected water content for optimum KF analysis.

which is accessible in the online titrations screen: Dependent on the expected water content.METTLER TOLEDO Good Titration PracticeTM in KF Titration Example: Expected water content: Optimum amount of water: Optimum sample amount: 5000 ppm 10 mg/sample 2g The Compact volumetric and colometric KF titrators support the user with a sample size calculation routine. 42 . an optimum sample weight range is recommended.

43 .1 Liquid samples When adding liquid samples. edible oils hexane. Rinse a 10 mL syringe 2-3 times with the sample Inject the sample using a 1 mL or 10 mL syringe through a septum cap. benzene glycerol.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6 Sample addition 6. 50 °C and fill it into a syringe. The syringe is heated together with the wax. Low water content Low water content Hygroscopic Viscous Very viscous ointments. In the case of a volumetric Karl Fischer titrator. Fill the 5 or 10 mL syringe with sample after removal of the piston. you must take suitable precautions to prevent atmospheric moisture from being absorbed. Store the sample in a bottle with a septum stopper to avoid moisture absorption from the air. ski wax. toluene. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. hydraulic oils. suppositories b c Liquefy the sample in an oven at approx. Inject the sample using a 5 or 10 mL syringe with a thick needle into the titration cell. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. creams. paraffin. aqueous emulsions. In the case of a volumetric Karl Fischer titrator. silicone oil. The following procedures are suitable for the different types of liquid samples: Sample characteristics High water content Low viscosity Examples perfumes. Inject it into the cell using a wide-bore needle. especially with samples of low water content. honey a Waxy candle wax. yoghurt. Possibly warm the sample slightly to lower the viscosity. mineral oils massage oil Procedure Inject the sample into the titration vessel either through a septum (KF coulometer) or through the needle hole in the three-hole adapter (volumetric KF titrator) using a 1 mL syringe with needle. This prevents the sample from solidifying in the syringe during the weighing. alcoholic beverages methanol.

Air flows through the molecular sieve into the bottle when you take a sample aliquot. the drop will adhere to the septum. use bottles with a septum stopper and pressure equalization. Start the titration. Place the syringe (upside down) in a beaker on the balance pan and tare the balance to "0". a vacuum develops in the bottle with septum stopper and it will no longer be possible to take a sample aliquot. Withdraw the plunger so that the drop at the tip of the needle is sucked back into the needle. If the sample is hygroscopic or has a low water content (< 1000 ppm). you must aerate the bottle with dry air (equalize the pressure).METTLER TOLEDO Good Titration PracticeTM in KF Titration Taking samples from a bottle with septum stopper After several samples have been taken. Start the titration method by pressing the <Start> button Inject the sample into the titration cell through the septum stopper. Fill a syringe without a plunger with molecular sieves. To avoid this. Sample addition of liquids with the back weighing technique – Fill the syringe to a quarter with sample. Fill the syringe with sample and wipe the needle with a paper tissue. Otherwise when the syringe is removed. Replace the syringe with the remaining sample on the balance and back weigh it. Enter the sample size in the titrator or transfer it automatically. Empty the syringe (into the waste bottle) and repeat the rinsing two or three times. seal it with cotton wool and insert it into the septum bottle using a short needle. – – – – – – – – – – 44 . Withdraw the plunger and rinse the syringe with the sample by shaking it.

pulverize less hard samples in a mortar. cooled analytical mill. jellied fruits. other methods have to be used for the determination of low water content by KF coulometry in solid samples: • • • External extraction External dissolution Drying oven On the other hand. If possible.g. – Add the sample with a weighing boat. Finely powdered Dusty Finely powdered with very low water content Soft – Use a weighing boat with an attached flexible tubing to add the sample: it prevents the sample from adhering to the wall of the titration vessel or to the electrode. 45 . For this reason. For instance. coarse-grained samples in a closed.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6. e.2 Solid samples It is not possible to directly titrate solid samples using KF coulometry .when the titration cell is opened to add the sample. it should be added under the same conditions as it was transported and stored. e. about 50-100 μg water enter the anode compartment. thus. crystalline samples: Weighing boat – Grind hard. The sample should be quickly weighed and added to minimize air exposure.g. salicylic acid. this would lead to an error of 5% to 10%.g. depending on the ambient humidity. cellulose powder: – Either weigh the sample in a dry box or extract it externally. Hard. Sample characteristic Brittle Hard/soft Pourable Procedure e. salts. fatty e. in a volumetric KF titrator solids can be directly transferred into the titration vessel. the storage of samples in a refrigerator may cause water to condense. jelly bears. chocolate. solid fat: – Grate the product and add the sample with a spatula. With an optimum sample size of 1 mg water/sample.g. almond paste: Cut into small pieces with scissors or a knife and add the sample with a spatula. it is necessary to warm up such samples to room temperature in a closed vessel before weighing.

suppositories: – Liquefy the samples in a drying oven at approx. Start the titration. The syringe is heated up together with the wax. Weight of solid samples with the back-weighing technique Weigh the sample in the weighing boat. Tare the balance to zero. Do not use a syringe. Back-weigh the empty weighing boat. chocolate cream.g. candles. edible fat: – Homogenize the sample well: the water is heterogeneously distributed. paraffin. inhomogeneous e. – Add the sample with a spatula. because the water is released if it is pressurized Waxy e.g. ski wax. - 46 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Soft. fatty. honey. to prevent the sample from adhering to the vessel wall or to the electrode. Add the sample into the titration vessel. The water content is often lower atthe surface than inside the sample.g. Enter the weight in the titrator or transfer it automatically. sugar products – The METTLER TOLEDO Visco-Spoon™ simplifies the handling with creamy samples since it can be directly mounted into the titration stand. This prevents the sample from hardening inside the syringe during the weighing process Creamy Highly viscous e. margarine. 50 °C and fill them into a syringe. butter. Use a weighing boat with attached flexible tubing if necessary.

almond paste (“marzipan”): Cut into small pieces with scissors or a knife. brittle Moderately hard. e. fruit juice extracts. Fibrous natural products Suspensions 47 . e. chocolate.g. noodles. cooled analytical mill. e. grain.g.g. then reduce it further with a homogenizer in an external solvent. brittle Viscous Hard. jellied fruits. minerals.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7 Release of water from the sample Karl Fischer titration is only possible if the water in the samples is freely available. dried fruit and vegetables. e. hard salts: Grind in a closed. e. e. water adsorbed on surface capillary bounded water (e. e. it is necessary to crush insoluble solids in order to gain access to the trapped water.g. The following methods are available: Sample characteristic Very hard Procedure e.g. Sample preparation Water: Example: Biological samples First of all.: • • • • entrapped water water of crystallization (salts). vegetable juices: Reduce with a homogenizer. inorganic salts. berries: Reduce with a homogenizer in an external solvent. organic salts. solid fat: Grate the product. crystalline products: Pulverize in a mortar. cheese: Hard. fatty Mince the product.g. suitable sample preparations and special Karl Fischer methods are necessary to release water in these samples.g. This is not the case with solids if the water is bound as. meat. e. pharmaceuticals Water Example: Food Example: Gypsum (Ca2SO4 * 2 H2O) Thus. sausage. fatty Soft. in plants) Water Example: Sugar.g. coffee beans: Crush in a mixer.g.g.

0 7. Water is then extracted providing the mixing time defined in the titration method is sufficiently long.9 srel / % 0.8 4. using either methanol or a mixture of it as the solvent.5 8.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.8 Solvent Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol 48 .8 1.2 1.1 Internal extraction Internal extraction is suitable for insoluble solids that release water quickly when crushed: – – Add the crushed samples into the titration vessel. You can speed up the extraction of water from the sample by • • In many cases.1 mg/pc 3. etc.3 2.8 1.9 0. Thermostatable vessel High–speed homogenizer Examples: Sample Flour Potato chips Ground hazelnuts Chocolate Instant coffee Dried chives Dried tarragon Aspirin Sweetener tablets Optical bleaching agent Result / % 12.g.4 1. the homogenizer eliminates the need to use auxiliary reagents such as formamide with.4 1.0 1. hazelnuts.9 0. heating the solution with a thermostating titration beaker.3 1.1 4. grinding the sample additionally with a built-in homogenizer (see photos below). sugar. potato chips.5 1. e.1 1.4 0.

2 External extraction External extraction is suitable for insoluble solids that release water only slowly when crushed as well as for samples with an extremely inhomogeneous water distribution. water is extracted from the sample by means of a defined quantity of solvent of known water content. the finely crushed sample is added to a solvent with very low water content and is left to stand until the water has been released from the sample. pepper. butter milk. 350 ppm) and toluene (max. The extraction of water can be improved • • • by shaking the solution (mechanical shaker. edible fat) for natural substances (almonds. shaking bath) placing the solution in an ultrasonic bath for a certain time or reducing the sample further with a built-in homogenizer. methanol decanol / octanol formamide for insoluble organic solids for fatty and dairy products (butter. Briefly. 49 . Provide sufficient solvent for the blank value determination so that enough solvent is available for the extraction.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. curry) for dehydrated products for sugar (total water). 600 ppm). Pay attention to the water capacity of chloroform (max. sugar and starch products for sugar (surface water) The organic solvents most commonly used are: • chloroform The external extraction is carried out in four steps: Step 1: Blank value determination of the extraction solvent Solvent in septum bottle Take a solvent aliquot Water content determination of solvent = blank value B - The water content of the solvent must be much less than the one of the sample. In particular.

METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 2: Weigh in solvent and sample Weigh solvent in = msolv Add sample Weigh sample = mext - Cut the sample into small pieces so that it releases its water more quickly and efficiently. Add a sufficient amount of sample. or use a homogenizer. A dilution factor of 10 . Step 3: Extraction - Shake. - 50 .20 is normally used. A mechanical shaker is normally used because the extraction time is often long (at least two hours or overnight). For the extraction of tablets. the addition of dry quartz sand has proven useful for improving and speeding up the extraction. the smaller the relative error because the total error is calculated with respect to the sample size. The larger the sample. or use an ultrasonic bath with heating. Shaking is the method generally used for extraction.

1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m . % or ppm). Amount of solvent (g) Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) The detailed calculations which lead to these formulas are given in the appendix.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 4: Allow settling. Water content of the supernatant extraction solvent (% or ppm) %: C = (VEQ*CONC-TIME*DRIFT/1000)*0. take an aliquot and titrate Allow to settle Take an aliquot of the extraction solution Titrate sample The following equations are used to calculate the water content of the extracted sample: ⎛ msol B ⋅ msol ⋅ ⎜C ⋅ − ⎜ mext mext ⎝ ⎞ ⎟ ⎟ ⎠ For % : R (%) = 100 100 − C For ppm : 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − R( ppm) = 6 ⎟ mext ⎠ 10 − C ⎝ mext Water content in the sample P (% or ppm). 51 . R: C: B: msol: mext: m: Note: Blank value (water content of the solvent.

6 72.5 0. The METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator are available with optimized method parameters for immediate execution. The weight of the solvent (msol).4 0.6 61.2 Chloroform Volumetric KF Titration Sample Result / % srel / % Extraction solvent Cheese Liver sausage Mustard Chicken broth Tobacco Wool Acrylic paint 27.9 11.4 0.6 0.4 4.3 0.4 0. The solvent blank is determined directly from the method running in standby by pressing the ‘Start blank’ button.5 Decanol:formamide:methanol 8:2:1 Decanol:formamide:methanol 8:2:1 Decanol:formamide 1:1 Decanol:formamide:methanol 8:2:1 Methanol Methanol Formamide There is a dedicated KF method type ‘External Extraction’.5 9.8 54.METTLER TOLEDO Good Titration PracticeTM in KF Titration Examples for the external extraction: KF Coulometry Sample Result / ppm srel / % Extraction solvent Sucrose (surface water) 72 4. the weight of the sample (mext) and the weight of the aliquot of the supernatant solution containing the extracted water (sample size m) is entered into the respective sample data fields: 52 .3 0.

e. The amount of sample should be sufficiently large to ensure that the amount of water in the sample is significantly greater than that in the solvent prior to extraction. in order to maximize the extraction effect and ensure that the difference between the water contents before and after extraction is as large as possible. for instance. The amount of sample should also take account of the absorption capacity of the solvent. 3. “External extraction”) in the method function “Calculation”.METTLER TOLEDO Good Titration PracticeTM in KF Titration The equation for the calculation of the water content of the extracted sample is predefined in the calculation method function. In particular. The water content of the solvent should be as low as possible. 2. by selecting the appropriate calculation (i. Note: 1. reaches the saturation limit for water already at 350 ppm! 53 . Chloroform. the formula is automatically given.

%: C = (VEQ*CONC-TIME*DRIFT/1000)*0. only the calculation method function has to be adapted to by selecting the corresponding calculation from the list of proposed results.8 2. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % AND ppm: R: C: Water content in the sample P (% or ppm) Total water content (sample + solvent). or with a high water content Pure solvents can be used to dissolve the samples.2 1. External dissolution is suitable for soluble solids with an extremely inhomogeneous water distribution. The dedicated method type ‘External Extraction’ and the METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator can be used as templates. the addition of methanol is not necessary. waxes and suppositories Example: Sample Result / ppm srel / % External solvent Sucrose (total water) Naphthalene Phenol Salicylic acid Contact adhesive (“Rubber cement”) 533 35 174 116 278 4. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) 54 . ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%. in % or ppm.3 External dissolution External dissolution is defined as the complete dissolution of a sample in a defined amount of solvent of known water content.9 5.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.3 formamide methanol methanol methanol chloroform The method corresponds to external extraction except that the sample dissolves completely in the external solvent.1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m B: msol: mext: m: Blank value (water content in % or ppm) of the solvent. The following solvents are commonly used: • • • • methanol formamide chloroform toluene for organic solids for sugar products for petroleum oils and adhesives for tar. or with a very low water content.2 10.

Remove approx. Since you are able to work with larger amounts of sample when working with this technique. 3.20 mL of anolyte titrated to dryness into the syringe. serum. weigh it and inject it into the titration cell. this error is reduced. KF coulometry is not suitable for samples with water contents of 10-100% because a very small amount of sample would have to be used. 2. Determine the weight of anolyte injected by back weighing.4 Lyophilized substance in septum bottles The extremely low water content of freeze-dried substances (e. In fact. 7. Direct titration is not suitable. 5. Rinse the syringe two or three times in this way.METTLER TOLEDO Good Titration PracticeTM in KF Titration To obtain accurate results a large sample amount is used for substances with an inhomogeneous water distribution. because a large sample amount leads to a too long titration time. foodstuffs) in septum bottles means that external extraction or external dissolution as described in the previous sections are not recommended. If the solid has a low water content (<200 ppm).g. and too much titrant is consumed. the blank value correction is too large compared to the amount of water in the sample. Draw 10 . Draw an aliquot into the same syringe again. On the other hand. Determine the weight by back weighing. If 1 g of sample has a water content of 100 ppm (= 100 µg) for instance. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. 4. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. the error as a result of opening the titration stand will be between 10 and 30 µg. Thus. 7. You should therefore proceed as it follows: Take an aliquot of anolyte Inject it in the septum bottle Shake Take aliquot and titrate Procedure: 1. weigh it and inject it into the septum bottle. 6. 55 . biological tissue. the error obtained by direct titration if the titration stand is opened to add the sample is too large. the sample is previously diluted through external dissolution to be able to titrate a larger sample aliquot.

7. 6. neither the calculation for the external extraction nor for the external dissolution are needed for this procedure using the volume instead of the mass. 56 . Rinse the syringe two or three times in this way. With a standard method calculation and calculate the water amount in µg. Remove approx. If you know the lyophilized sample amount in the septum bottle. the water amount in the septum bottle is 4 times larger. because the anolyte titrated to dryness has a blank value of "0".METTLER TOLEDO Good Titration PracticeTM in KF Titration If the sample is completely dissolved: use the method type “External extraction” and the calculation for the "External dissolution" If a suspension is formed: use the method type “External Extraction” and the calculation for the "External extraction" Note: In both cases. The accuracy of a plastic syringe is enough. 2. 8. the final result must be multiplied by 4 (factor f = 4). Alternative procedure: 1. Since ¼ of the total amount was injected. In this way. The water amount in µg is determined. then you can additionally calculate the result can be given in ppm. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. 3. Draw exactly 5 mL from the septum bottle into the same syringe again and inject it into the titration cell. 4. Draw exactly 20 mL of anolyte titrated to dryness into the syringe and inject it into the septum bottle. Thus. 5. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. zero must be entered for the blank value (B).

Calculate the volume from the time and the gas flow rate.CO2 gas can not be titrated directly since iodine reacts with CO2. .g.If possible.Add a sufficient amount of buffer solution into the titration vessel to determine the water content of acid gases such as e. . . Determination .Stop the gas flow after 1 to 2 mL titrant has been consumed. 600 s as termination parameters.Purge the system with the gas before you start the determination. . . . hydrochloric acid.As soon as the drift is stable again. . Three-way valve Flow meter Gas Control valve The flow rate has to be constant to determine the volume necessary to calculate the water content: gas volume = gas flow rate x time. you should titrate the gas sample directly from the source. . the gas must be directed through the titration vessel for a defined period of time.Turn the three-way valve. . .5 Determination of water in gases To determine the water content of gases.Select "Max. start the titration and reset the three-way valve to its original position in order to direct the gas into the titration vessel. The gas must be directed through a water-dissolving. depending on the water content of the gas.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. to prevent the gas from flowing into the titration vessel.With sample vessels the gas amount gas can be determined by differential weighing. Notes .g.Purge the sample vessel and the tubings thoroughly beforehand with the gas. time" and a "Delay time" of e. Sampling/sample addition . The water contained in the gas is then absorbed by the liquid and can be determined by means of Karl Fischer titration in a process similar to external extraction. evaporated methanol lost in the gas stream must be replaced depending on titration time and number of determinations. If not.Adjust the gas stream to a constant flow rate with the control valve: 50 to 200 mL/min. you must fill the gas either into special gas sample tubes or into small steel cylinders. to ensure that the titration is terminated after the maximum time. 57 .When titrating large quantities of gas in the same solvent. water-free absorption liquid in which CO2 itself does not dissolve. The water content in ppm is calculated by entering the volume and the density.

cause side reactions with the Karl Fischer reagent. inorganic samples.1 bar (cf. If you use air for organic samples.6.g.0 mg/L Therefore. Air should therefore only be used for non-oxidizable.6 Determination using the drying oven This method is suitable for solids and liquids that 1.2 Purge gas Air contains oxygen. If you use nitrogen from a gas cylinder. the oven temperature should not exceed 160 °C.4 – 8.7 500 97.9 166 99. cf.6. The water is transferred to the titration cell in a current of dry inert gas (purge gas).METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. causing the water in the sample to vaporize. chapter 7. or 2. e. 58 .6.5 .4) A gas stream of approx. Experiments with various gas flow rates yielded the following results: Gas flow rate Recovery [mL/min]: [%]: 108 99. 7. 150 mL/min is ideal for DO308 and 70 mL/min for Stromboli (automated KF drying oven.1 Principle The sample is heated in an oven. Thus. 7.1 - The recovery rate is clearly decreasing with increasing gas flow rate. the purge gases must be first dried before entering the KF oven. and the amount of water is determined. 11 mg/L nitrogen gas from a cylinder: 1. For Karl Fischer titration. for accurate results do not select a too high gas flow rate. you should use a two-stage pressure regulator so that the final pressure is in the range 0. The purge gases commonly used contain moisture. which could react with the sample at higher temperatures. the residual moisture in the purge gas should be less than at least 10 μg/L (for coulometric determination) and 20 μg/L (for volumetric KF titration) in order to obtain accurate and repeatable results.5).6. that release water very slowly. chapter 7.: o o air with 50% humidity: approx.

in contrast to other desiccants. they are rapidly exhausted. the vaporization is often very irregular. especially methanol. Start off with the silica gel to absorb the bulk of the water and then use molecular sieves to reduce the residual moisture to a minimum.e.60 s). In the case of KF coulometers. The short mix time is necessary so that a delayed vaporization of water does not lead to premature termination of the titration. whereas molecular sieves requires temperatures up to 300 °C. This is caused by a slow release of the final traces of water or slow thermal decomposition of the sample. With some samples the drift at the end of the titration is significantly higher than the initial drift. Method 2: The water is first vaporized and then titrated afterward During a defined long mix time. all the water is vaporized and transferred to the titration cell. you should set the maximum titration time as the termination parameter (i. deactivate the drift stop). 7. deactivate the drift stop). but their water absorption capacity is low. Silica gel is appreciably better in this respect.METTLER TOLEDO Good Titration PracticeTM in KF Titration Several agents are available to dry the purge gas: Method Residual moisture Residual moisture for 200 mL/min gas flow rate (drift) Sulfuric acid.e.6. Method 1: The water evolved is continuously titrated After a short mix time (20 . The KF titration is then started. To ensure that the determination is repeatable. In such cases you should use the maximum titration time as termination parameter (i. Silica gel and molecular sieves have the advantage that they can be regenerated.80 µg H2O/L 40 . 100% Phosphorous pentoxide. Passing the gas stream into the titration cell causes the anolyte (in the KF coulometer) and solvent (generally methanol in KF volumetric titrator) to vaporize.e. The amount depends on the gas flow rate and the type of KF reagent present in the titration cell. there are two types of anolyte solutions: 59 . Silica gel can be regenerated over night at 150 °C.3 Procedure There are two different methods to perform a KF titration with the drying oven: 1. The relative drift stop or the maximum titration time can be used as the termination criterion. the titration starts and the released water is continuously titrated. In order to avoid the latter you may also use the minimum time as termination parameter. i. At the end of the titration. 2. P2O5 KF one-component reagent Silica gel Molecular sieves 3 Å 50 . It is therefore recommended to dry the gas with a combination of silica gel and molecular sieves.50 µg H2O/L 15 – 20 µg H2O/L 50 – 60 µg H2O/L 5 – 10 µg H2O/L 10 – 15 µg H2O/min 8 – 10 µg H2O/min 3 – 4 µg H2O/min 10 – 12 µg H2O/min 1 – 2 µg H2O/min You can use the following desiccants to dry the purge gas: – – Molecular sieves are the best drying agent as far as residual moisture is concerned.

oven temperature 200 °C: approx. 7.e. dedicated anolyte to be used with a KF Oven (e. time 60 . oven temperature 200 °C: approx.METTLER TOLEDO Good Titration PracticeTM in KF Titration – Standard anolyte solutions containing methanol (e.g.e.7 99.2 1.9 9. 3.9 2. Make sure that the level of the anolyte does not fall below that of the catholyte (higher drift!).5 mL/hour Anolyte containing ethylene glycol.200 mL/min. there is a small loss of water. time Max. of samples srel / % T /°C Time/min Comments Polyamide Polyethylene Motor oil Cement Cooking salt Carbon black 5547 68 842 8200 360 3583 6 6 6 6 5 5 0.6.2 99. fibers) or with samples of low water content. i. As an example data from coulometric determinations are indicated here below: Method Anolyte Gas flow rate Recovery / % 1 1 2 2 Coulomat AG Coulomat AG Oven Coulomat AG Coulomat AG Oven 166 mL/min 183 mL/min 166 mL/min 106 mL/min 99. the recovery is not 100%.2 4. The recovery therefore depends on the amount of methanol vaporized and the method used. Examples: Sample Result / ppm No.8 6.g. and the better the recovery.5 . An air pump is available as an optional accessory. It has a large glass sample boat capable of holding up to 10 cm3 of sample.200 mL/min. time Max.g. as well as a gas flow meter. Due to the vaporization of the methanol. you should replace the anolyte lost through vaporization with new anhydrous methanol. This is particularly important with low-weight samples (e.95 98. Coulomat AG or CombiCoulomat frit): Anolyte loss at 150 . time Max.5 190 280 140 300 300 200 15 10 15 20 10 15 Max. The DO308 oven is equipped with a gas drying unit with two bottles for silica gel and molecular sieve. 1 mL/hour – From time to time.4 Manual Karl Fischer drying oven The METTLER TOLEDO DO308 drying oven can be operated in a temperature range from 50 to 300 °C. time Max.4. the faster the water is titrated. The procedure for the determination of water content is described in the operating instructions. time Max. Coulomat AG Oven): Anolyte loss at 150 .1 Briefly: The less methanol is vaporized. i.

This leads to a too low result. replace the silica gel and molecular sieves of the gas drying unit.55% or VWR/VWR/MERCK water standard KF oven 1%. In such cases.5 to 4 mL/h for an oven temperature of 200 °C and a flow rate of 200 mL/min. Close the stop cock and purge the "hot zone". Open the stop cock. A large amount of evaporated water cannot be fully absorbed by the solvent. For instance. To check the performance of the titrator/drying oven system. Some samples require some time before water starts evaporating. If the water is titrated as soon as it begins to evaporate. in volumetric KF titration the methanol loss is approx. . you may use the SIGMAALDRICH HYDRANAL® water standard KF oven 5. 6. Here a short mixing time (15 to 60 s) or the minimum titration time should be defined to prevent the titration from being terminated too early. The evaporation is reduced by adding ethylene glycol (higher boiling point) to a maximum solvent ratio of 20-30%. the evaporated solvent lost in the gas stream has to be replaced. Coulometer KF: The internal drying tube of the generator electrode has to be replaced with an external. For the same reason. the recovery increases to 99. Add the sample through the tapered joint and slide the glass boat with the sample into the oven: Guide rod with magnet Slider Glass sample boat 8. and does not drop into the cathode compartment/ titration cell. If the drift is constant. 5. Set a gas flow rate of 150-200 mL/min. 2. purge the "cold zone". If several determinations are performed in the same solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments: 1. 3. 10. do not select the parameter "Auto start". The drift should be 5-10 μg H2O/min at a gas flow of 150 mL/min. If the drift is higher than 15 μg H2O/min. start the titration so that the drift value is automatically entered. bent drying tube. This can happen when the titration is started only after complete evaporation. and/or replace the anolyte of the KF coulometer.7%. Experiments using methanol as the solvent gave a recovery rate of 98% for a stream of 166 mL/min. Some samples have surface water that is lost as soon as the oven is purged with dry gas. Always start the titration before you place the sample in the oven to ensure that the correct drift value is adopted by the method (online drift). you should proceed as follows: 7. Then. evaporated solvent does not condense in the drying tube. 61 9. 3. 4.

the lift is moved downward and gravity facilitates the removal of the sample vial from the oven. 62 . The drying oven can be operated in the temperature range from 50 to 300°C. STROMBOLI is completely controlled by the titrator: all the parameters for the determination. After the analysis. 2.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. including the oven temperature.5 STROMBOLI automatic oven sample changer The METTLER TOLEDO STROMBOLI oven sample changer is a drying oven for automatic Karl Fischer titration with the KF Compact Volumetric V30 and Coulometric Tititrators C30 as well as with the Titration Excellence Titrators T70 and T90. STROMBOLI offers one fixed place on the sample rack for an empty sample vials in order to determine the drift value. while a glass tube pierces the aluminum foil cover. 3. Besides 14 places for glass sample vials. 1 During a sample series: 2 3 1. The blue rubber cap seals the sample vial tightly against the oven. The sample vials are moved upward into the oven by a lift. The purge gas flows through the sample vial and the water vaporized is transported via the transfer tube into the titration cell of the coulometer. are included in the titration method. The oven heats the sample to the set temperature.6.

g. The drift value is defined as the moisture entered into the titration cell by the purge gas. The sample vials are sealed with self-sealing aluminum foil and a rubber cup. This takes 10-20 minutes as can be seen in the following diagram: 63 . This is particularly important with light samples (e.METTLER TOLEDO Good Titration PracticeTM in KF Titration Sample vials: Rubber cap Aluminum foil Sample vial The glass sample vials have a large volume (up to 25 mL). To determine the drift value accurately. Drift determination: The drift determination is performed with an empty vial on the first position of the sample rack. the moisture in the empty sample vial has first to be removed. fibers) or with samples of low water content.

e.) are always slightly different. This means that the stored drift value of the previous determination will be used. If this is the case. If. If the maximum titration time is used as termination criterion in the method -which is what we recommend. for example. > 15 μg H2O/min). If the temperatures of successive loops are different. Performing the drift and blank value determination In general. whose optimum bake-out temperatures differ. they can be measured at different temperatures using the same method.e. a blank value determination should be performed before each series of samples since the ambient conditions (humidity. Multiple sample series at different temperatures Several series can be started on the same sample turntable – even at different temperatures. Nevertheless. and the adsorbed moisture on the glass walls of the vial) minus the amount of water due to the drift (i. With rapidly changing. etc. At the start of the method. Thus. These method templates are based on a dedicated KF method type called ‘Stromboli’. the moisture content is somewhat lower. different plastic samples have to be analyzed. Important: After a blank value determination. a drift determination should still be performed at least once a day in order to check whether the drift is too high (e. The blank value can also vary as a function of temperature. 64 . the blank value determination also takes the actual drift into account.e. several blank value determinations can be performed one after the other in the same loop and the mean value calculated from the results. In this case.e. i. a blank determination can be performed between two sample loops. the moisture in the air present in the vial. The blank value should be determined before each series because the humidity can change. It is therefore not necessary to perform a drift determination before each series. To determine the blank value as accurately as possible. The new blank value is automatically used for the blank correction. you can check whether the drift is constant and the new drift value can be used for the next series. In the same way. drift value x time). The optimum blank value is in the range of 70 . the silica gel and molecular sieves in the bottles of the gas drying unit can be replaced. you can enter the number of samples the series includes for each loop.the analysis times for the determination of the blank value and for each sample are the same. There are dedicated METTLER TOLEDO multi-loop methods available in the V30 (M313) and in the C30 (M396). and thus the moisture adsorbed on the glass walls is not always the same. it is important to use a new sample vial for each blank value determination (i. For each series.METTLER TOLEDO Good Titration PracticeTM in KF Titration Blank value determination: The blank value is the amount of water contained in an empty sample vial (i. the drift value can change with time.g.300 μg water. the last sample vial that was baked out remains in the oven until the temperature has stabilized at the temperature of the next loop and the drift is low and stable. the method contains a so-called sample loop. suboptimum conditions. In this case. moisture in the sample vial. as well as the anolyte in a coulometric analysis. the vial used no longer has the same properties as the "fresh" sample vials. gas flow. at the end of a series the blank value can be measured again and compared with the value determined at the beginning. The loops run through one after the other and the samples are processed sample for sample. The first sample of the next loop is then transferred into the oven and the water determination begins. By performing a drift determination at the end of the series or between several series. one with the same properties as the sample vials into which the samples have been filled in).

A special (longer) gas inlet glass tube is provided to bubble gas into the liquid. 2. and therefore it does not drop into the cathode compartment. Vials that have undergone different treatment can show differences in the blank value of 50-150 μg water. These are partially vaporized (e. Use the same vials for a sample series as well as for the blank value determination. This valve shall be used especially if inert gas sources are used. you can not only determine solids but also liquid samples. Allow sample vials that have been used or cleaned to stand overnight in the atmosphere for conditioning before starting measurements. KF Coulometer C30: The internal drying tube of the generator electrode has to be replaced with an external. evaporated solvent is not condensing in the drying tube. that the inert gas stream to the gas source is closed and the system is ventilated with ambient air. The amount of moisture adhering to the glass surface of the sample vials strongly depends on how the vials were treated beforehand (cleaning.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments on the operation with the STROMBOLI oven sample changer: 1. toluene.55% or VWR/VWR/MERCK water standard KF oven 1%. bent drying tube. In this way. This has a large effect on the blank value and thus on the result. This is necessary so that the KF solvent or anolyte is not aspirated into the hot sample vial if Stromboli is not properly shut down while it is still hot. 7.g. Set a gas flow of 40–60 mL/min. 4. To check the titrator/drying oven system. An optional 3/2 way valve which is automatically controlled by STROMBOLI can be used instead of the T-piece mentioned in 1. The delivery tube has a T-piece that causes a small leak flow. 8. A sudden shutdown of power immediately switches the valve in that way. This test also serves to check the tightness of the oven and the connection tubing 65 . motor oil) or completely vaporized (e. you can use SIGMA-ALDRICH HYDRANAL® water standard KF oven 5. drying and storage). Therefore no precious inert gas is lost and no vacuum is applied to the system which may result in a back aspiration of the anolyte into the hot oven.g. 5. 6. 3. see also list of results). With STROMBOLI. since it provides a leak free inert gas stream during normal operation.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

Examples:
Sample Result [ppm] No. of samples srel [%] T [°C]
Max.Time

[s]

Comments

Polylactic acid 0.5 g Polymer ABS-50 T 10014 3g Polymer ABS-50 F10014 2g Motor oil 1120/03 (AA) 2g

2589

3

1.1

160, air 190, N2gas 170, N2gas 165, air

--

Stir time: Max. time: rel. drift:

600 s 300 s 3 µg/min

736

5

1.1

300

Stir time: 900 s Delay time: 300 s Stir time: 900 s Delay time: 300 s Stir time: 60 s Delay time: 300 s Very slow evaporation, not faster with 180°C, above 180°C decomposition Stir time: 60 s Delay time: 300 s Very slow evaporation, above 180°C decomposition

1312

13

0.9

300

241 261

3 4

4.4 7.9

1500

Motor oil 1034/03 (AA) 1.5 g

426 438

4 3

2.7 4.5

180, air

1800

66

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

8 Measurement results
8.1 Resolution and detection limit
The following table indicates the theoretically smallest increments of current (KF coulometric) and titrant (Volumetric KF) which could be achieved by the instruments based on their technical specifications. Therefore, these are indicative values and they should be considered as such:
C20/C30 Compact Coulometric Instrument V20/V30 Compact Volumetric Titrator Resolution: 20’000 burette steps
5 mL burette: 0.25 µL c=5 mg H2O/mL: 1.25 µg H2O/step

Theoretical smallest increment

0.1 mC
Theoretical: Resolution:

(100 mA x 1 ms)
0.01 µg H2O < 0.1 µg H2O

Detection limit (limit of detection, LOD)

10 µg
Example: 10 g sample → determ. of 1 ppm Assumptions: - Current is used for iodine generation - Generated iodine is reacting 100% with water only.

50 x resolution
5 mL burette: 12.5 µL c=5 mg H2O/mL: 62.5 µg H2O Example: 5 g sample → determ. of 12.5 ppm

The theoretically smallest current increment that can be generated by the C20/C30 Compact Coulometers is 0.10712 mC which corresponds to 0.01 μg water. However, the achievable resolution of the instrument is in the order of less than 0.1 µg H2O, whereas the detection limit (also called “limit of detection”) is approx. 10 μg water per sample. Thus with a 10 g sample, 1 ppm water can be determined. For the V20/V30 Compact Volumetric instruments, the detection limit mainly depends on • • • The resolution of the burette drive, i.e. the max. number of steps which can be achieved by the stepper motor. the burette volume size; generally, a 5 mL burette is used for volumetric KF titration. The concentration of the titrant.

8.2 Measurement accuracy
The accuracy strongly depends not only on the technical specifications of the instruments, but also on the several factors that have been already mentioned in the previous chapters: 1. Sampling (including suitable storage, if necessary) 2. Sample treatment and preparation 3. Expected water content and selection of suitable instrument 4. Selection of optimum sample size 5. Condition of the KF reagents, i.e. fresh reagents, pre-titration, low drift value, … 6. Sealed titration vessel and tight tubing, 7. Condition of the indication electrode 8. Coulometry: condition of the generating cell 9. Parameter settings in the titration method etc. 67

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

To determine the closeness of agreement between the result of measurement and the true sample value, measurements can be performed either by titrating water standards or by titrating samples with known water content. The measurement accuracy depends on all the various factors described and explained in the previous sections. The crucial factors are optimum control as well as the water content and the amount of the sample.

8.3 Repeatability
The closeness of the agreement between the results of successive measurements of the same sample can be expressed quantitatively as the relative standard deviation, srel, given as %. With optimum sample amount and control, the following values can be obtained under test conditions for repeatability. The graph shows the relative standard deviation for different water contents. In general, the repeatability of a sample series becomes worse with decreasing water content. Note that for water content below 10 ppm it is not recommended to use a volumetric technique.

100% 10% 1% 1000 ppm 100 ppm 10 ppm 1 ppm

Coulometry
Not suitable for coulometry

Volumetry
srel < 0.5 %

srel < 0.5 %

srel 5 - 0.5 % srel 5 - 0.5 % srel > 5 % srel > 5 %
Not suitable for volumetry

In the following graphs, the relative standard deviation srel (%) of several series with different water content are given as a function of the sample size:

68

sample size for different water contents: KF Coulometry KF Volumetric Titration: srel (%) 6 110 ppm 5 330 ppm 4 720 ppm 3 2 1 0 0. it is necessary to use the optimum sample size in order to achieve precise results.METTLER TOLEDO Good Titration PracticeTM in KF Titration Relative standard deviation srel vs.0 2. A good repeatability is achieved the sample size is increased particularly for low water content values. 69 .0 5.0 Sample size (g) In both cases.25 0. with decreasing sample size the relative standard deviation srel becomes worse. Therefore.0 3.5 1.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

9 Interferences
9.1 Effects of temperature
Temperature effects on the KF titrant The Karl Fischer titrants consist of approximately 90% methanol or ethanol. Their volume increases considerably if the temperature increases, and their concentration decreases accordingly. S. Eberius [3] specifies a correction factor of 0.0012 per degree Celsius for methanolic Karl Fischer solutions. According to ISO 760, a temperature increase of 1 °C causes a drop of 0.1% in the concentration. The titrant (in particular, the two-component KF solvent) may loose sulfur dioxide if the temperature rises. This causes bubbles to form in the titrant tubing, an effect which is worse the faster the rate at which the burette is filled. These titrators allow you to define the filling rate of the burette separately for each titrant, e.g.:
Temperature / °C < 15 15 – 30 > 30

Filling rate for one-component KF volumetric titrant / % Filling rate for two-component KF volumetric titrant / %

100 80

100 60

70 40

Titration at low temperatures You can perform Karl Fischer titrations at low temperature to eliminate undesired side reactions. The water content of peroxides, for example, can be determined at -40 °C. You must use the two-component reagent to do so, because the reaction rate of the onecomponent reagent is too slow at this temperature. Titration at high temperatures Increasing the titration temperature speeds up the dissolution of the sample or the extraction of the water from it, resulting in shorter titration times. Titrations at elevated temperature have proved particularly effective for foodstuffs, e.g. sugar, flour, potato flakes, hazelnuts, custard powder. The maximum temperature depends on the boiling point of the reagent (boiling point of methanol: 64 °C, boiling point of ethanol: 78 °C).

9.2 Side reactions
Side reactions that falsify the results can occur parallel to the Karl Fischer titration. There are mainly three side reactions that can affect the result: 1. Reaction with methanol, CH3OH Aldehydes and ketones react with methanol leading to additional water Esterification with carboxylic acids leading to additional water Ketones and aldehydes react with sulphur dioxide, a base and water (i.e. water is consumed) The reaction of iodine with e.g. oxides, hydroxides, carbonates, amines, ascorbic acid, and mercaptans leads to a higher consumption of iodine giving higher water content.

2. Reaction with water, H2O

3. Reaction with iodine, I2 -

70

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

9.2.1 Reaction with methanol
Aldehydes and ketones: Methanol, CH3OH, reacts with aldehydes (R-CHO) and ketones (R-CO-R) to form acetals (CH3-CH(OR2)2 , and (CH3)2C(OR2)2 respectively, the latter also called ketals), as well as water: Formation of acetals:

CH3CHO + 2 CH3OH
Formation of ketals:

→ →

CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O

(CH3)2CO + 2 CH3OH
Solution: -

Use the special reagents for aldehydes and ketones with these substances (so-called K-reagents). They contain other alcohols than methanol. - Experiments have shown that the side reaction still takes place despite these reagents. Each time acetone is determined, for example, the drift is higher than before the titration: the larger the sample, the greater the drift increase. It is therefore recommend to perform the determination with a small sample amount and to replace the solvent after two or three samples. Esterification: Methanol, CH3OH, reacts under presence of strong acids (i.e. sulfuric acid) with carboxylic acids (R-COOH) to an ester (R-O-CO-CH3) and additional water:

R-COOH + CH3OH →
Solution: -

R-COO-CH3 + H2O

First neutralize the sample using a suitable base (imidazole) before KF titration.

9.2.2 Reaction with water
Another side reaction, the bisulfite addition, occurs with aldehydes and ketones in the presence of SO2. Water is consumed in the process. Bisulfite addition:

CH3CHO + H2O + SO2 + NR R1-CO-R2 + HSO3Note: SO2 + H2O = HSO3- + H+ Solution:

→ →

HC(OH)SO3HNR R1(R2)C(OH)SO3-

- Start the titration immediately after adding the sample. - Perform a fast titration by predispensing 90% of titrant consumption This causes the water to be titrated quickly, before any bisulfite addition can take place. The "Autostart" parameter allows for the automatic start of the titration as soon as the sample has been added and water is detected.

9.3 Reaction with iodine
The Karl Fischer reaction is a REDOX reaction with iodine as the oxidizing agent. Thus, iodine may also react with readily oxidizable samples. On the other hand, iodine can also be reduced by SO2 in some samples such as e.g. oxides. Both reactions cause additional iodine being consumed, giving a false higher water content.

71

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

The following substances can react with iodine:
Ascorbic acid Boric acid, H3BO3 Disulfite, S2O5 2– Hydroxide, OH– Mercaptans, R-SH Peroxide, R-O-O-R Sulfite, SO3 Tin(II) salts
2–

Arsenite, AsO2 – Tetraborate, B4O7 2– Iron(III) salts Hydrogencarbonate, HCO3– Nitrite, NO2
– 2– 2–

Arsenate, AsO4 3– Carbonate, CO3 2– Hydrazine, N2H4, and its derivatives Copper(I) salts Oxides, e.g. CaO, MgO, MnO2 Silanols, R3-Si-OH Thiosulfate, S2O3 2–

Selenite, SeO3 Tellurite, TeO3

Solution: The Karl Fischer titration for the majority of these substances can be performed with the aid of the drying oven, or also by performing an external extraction.

9.4 Example: reevaluation of side reactions
The water content obtained is too high if side reactions previously described have occurred. This can also be the case if a drying oven is used, and the sample slowly decomposes. Nevertheless, the correct result can be reevaluated by graphical extrapolation. Example: Water determination in red polypropylene fibers.
µg water

250 °C 160 °C 120 °C

300 200
115 mg 640 ppm

100

0

5

10

15

20 min

The determination was carried out for a period of 20 minutes (max. time) with the drying oven set to 120 °C, 160 °C and 250 °C. The following results were obtained:

120 °C 1186 ppm

160°C 1442 ppm

280°C 1955 ppm

The volume-time curve clearly indicates the occurrence of a side reaction, which becomes faster with increasing the temperature. The "water content" increases with temperature. By reevaluation using the LabX® titration PC software the actual water content can be obtained by extrapolating the titration curve to time t = 0 min (green dotted lines). The content is 115 mg water; this corresponds to a water content of 640 ppm for a sample weight of 0.18 g. The extrapolated result was confirmed by an external extraction in methanol. In fact, the result obtained with this method was 610 ppm.

72

Level of anolyte should be higher than that of the catholyte . titration never ends Very long pretitration Poor repeatability Wet anolyte .Clean the platinum pins of the measurement electrode with paper tissue . if possible increase amount of sample Wrong sample preparation and sample addition .Higher oven temperature . drift stop .Replace anolyte Amount of sample too small .Check whether titration stand is completely tight.Check whether titration stand is completely tight.Replace anolyte .Measurement electrode is faulty Titration stand not protected against moisture .Use t(max) as termination parameter .Use rel. e.Use smaller sample Long titration time.Homogenize sample.Lengthen vaporization time (increase t max) . . drift stop as termination parameter. .1 Coulometry Problem Possible causes and action to take Anolyte is not bright yellow but dark yellow to brown Drift is too high after the pretitration of a fresh anolyte .METTLER TOLEDO Good Titration PracticeTM in KF Titration 10 Troubleshooting 10.Use a different method Oven: water not completely vaporized . increase t(max) Wrong control parameters . . especially at low water content (< 1000 ppm) 73 .g.Replace silica gel and molecular sieve in the gas drying unit The drift remains too high during standby titration Drift is too high after the titration of a sample Side reaction with the anolyte .Use higher oven temperature .Replace molecular sieves and silica gel in drying tube .Increase value for rel. Oven: .Increase vaporization time.Increase end point Oven: water vaporizes very slowly and irregularly .Add a small amount of one-component KF titrant to the catholyte. 1 mg water per sample is present. Water distribution in the sample is not homogeneous .Measurement electrode is not plugged in .The repeatability is strongly dependent on suitable sample preparation and sample addition.Grease the tapered joints Moisture from cathode compartment and diaphragm .Increase amount of sample to ensure that approx.Clean titration cell and generator electrode and dry at 50 – 80 °C .

Too high value: see above “too high value” . bad repeatability With water standard 1.Use higher oven temperature . It has no influence to the result.Sample not thermal stable: Use lower oven temperature .Replace or repaire generator electrode. Checking drying oven Out of limits. Sample not dissolved (emulsion) . If the sample preparation and addition is not done carefully.Check drift and blank value .Use back weighing. 10 – 15 minutes .Add chloroform or another solvent (maximum of 30%) to the anolyte to dissolve the sample Oven: .METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .Too low value: see above “too low value” if this does not help. if it is defective.Replace anolyte If this doesn’t help.0 or 0.Use start cautious Oven: .0.Clean titration cell and measurement electrode Poor sample preparation and addition Samples of low water content (< 1000 ppm) are always hygroscopic.use a bigger sample size up to 0. contamination with atmospheric moisture occurs.2 . do not splash to the walls of the cell.Extend tmin (minimum titration time) Incomplete sample addition .Lengthen vaporization time (increase t max) .Use smaller sample size Values too high The titration was too fast → overtitration . For samples with very low water content < 30 ppm . at 170 °C.Reduce the value for rel.Use fix generator current 100 mA .Replace anolyte . Anolyte has too low conductifity .1 mg/g .Add sample into KF reagents. bad repeatability Platinum parts of the generator are colored black Warning: “Conductivity too low” 74 . drift stop .Replace or change the anolyte . the Coulometer must be adjusted With water Standard KF Oven 1 %. . check generator electrode.3 g Generator electrode is contaminated The black cover cannot be removed.Sample is oxidized: use nitrogen as a purge gas Checking coulometer Out of limits. .

Water distribution in the sample not homogeneous .Use "Rel. . external extraction.METTLER TOLEDO Good Titration PracticeTM in KF Titration 10. .Replace silica gel and molecular sieve in the gas drying unit Drift too high after titration of a sample The sample has not completely dissolved and continuously releases water . if possible increase amount of sample.see above Oven: . Side reaction of the sample with the KF reagent . titration never ends Wrong termination parameters .Use higher oven temperature .Increase oven temperature . .Reduce sample size Poor repeatability of the results Amount of sample too small . Low water content (<1000 ppm)! .Replace molecular sieves and silica gel in drying tube .Extend tmax (maximum titration time) .Grease the tapered joints Condition Titration stand .Use different method.Check and optimize control parameters. drift stop" as a termination parameter. Titration stand not protected against moisture . drying oven.Increase vaporization time. increase t(max) Long titration time.g.Check whether titration stand is completely tight.The repeatability is strongly dependent on suitable sample preparation and sample addition.g. Wrong control parameters .Use t(max) as termination parameter .Increase value for relative drift stop. 75 . etc.Use longer mixing time or different solvents which dissolves the sample or extracts the water quicker.Clean platinum pins of the electrode with a paper towel.Extend vaporization time (increase t max) .Increase amount of sample to ensure 10 mg water per sample.Increase endpoint potential Oven: water vaporizes very slowly and irregularly . e.2 Volumetric Karl Fischer Titration Problem Possible causes and action to take Titrated solution is dark Drift too high after pretitration of fresh solvent Overtitration .Shake titration vessel The drift remains too high during standby titration Titration stand not protected against moisture .Homogenize sample. e. Oven: water is not completely vaporized .

which dissolves the sample.Reduce dVmax and dVmax factor.Increase sample size up to 0. Oven: .55 % at 220 °C.Replace solvent . The concentration determination is correct only if the di-sodium tartrate has completely dissolved. 0.Extend vaporization time (increase t max) .Use titrant with 2 or 1 mg/mL Oven: .Use higher oven temperature .Change solvent.Use back weighing.Change solvent or use fresh solvent after every sample.Reduce sample size Single values too high Control parameters too fast (= slight overtitration) . drift stop . If the sample preparation and addition is done carefully.0 is a simpler and a more dependable method. For samples with low water content < 400 ppm . Sample not dissolved .Samples of low water content (<1000 ppm) are always hygroscopic. . contamination with atmospheric moisture occurs.Extend tmin (minimum titration time) Incomplete sample addition . Di-sodium tartrate has only limited solubility In methanol max. Poor sample preparation and addition .Add chloroform or other solvent to methanol.12 g in 40 mL.METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .Replace the solvent frequently. bad repeatability 76 . With water Standard KF Oven 5. 15 – 20 minutes .Sample is oxidized: use nitrogen as a purge gas The results in a series are continuously decreasing Very slow titration with twocomponent titrant Wrong or greatly fluctuating values in the concentration determination with water Dissolving capacity of the solvent is exhausted .Check drift and blank value . Determination of the concentration using di-sodium tartrate or Water Standard 10.Sample is not thermally stable: Use lower oven temperature .4 g Increasing value in the concentration determination with di-sodium tartrate Checking drying oven Out of limits. No more sulfur dioxide in the solvent . Water as standard requires practice The use of water for the concentration determination requires experience to obtain repeatable and accurate results.Reduce the value for rel.

V5 C20.V4. C0 V2.pyren e. C0 Peroxides V2. stearamide Weakly acidic: benzoic acid Strongly acidic: malonic acid. bitumen V4.V3. indole.V7 V2. nitrobenzaldehyde > C12 Stearyl alcohol. R-I R-NCO Benzophenone Method V2. anthracene. C0 V2 C20 V15 Low pKa value: phenol.1 Solid samples 11. nitrotoluene. salicylic acid High pKa value: 2-chlorophenol. C0 Esters Carboxylic acid ester R-COOR´ Carbonic anhydride ROCOOR´ 77 .V5 C20.V4. C0 Sulfur compounds Phenols V0. naphthalene > C20 Tar. V4 C20 V2.V4.1 Organic Chemicals Substance Acetals Aldehydes Mono-/polyalcohols Amines Examples R1-CH-(OR2)2 Chlorobenzaldehyde.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11 Karl Fischer Titration: The Method at a Glance 11. nitrochlorobenzene Dialkylperoxide R-OO-R Alkylperoxide R-OOH Diacyl peroxide V0. o-cresol Side reaction: naphthol.V4 C20 Carbamates Carboxylic acid amides Mono-/polycarboxylic acids RO-CONH2 R-CONR´. V5 C20 V2. V4 V2. R-Br. V3.: benzamide.V3. C24 Hydrocarbons > C12 Biphenyl.g. C20 V11 C0 V2.V4. aminophenol Aromatic/aliphatic sulfonic acids sulfides R-S-R´ disulfides R-SS-R´ thiocyanates R-SCN V0.C22 V2.V3.1. V3.V5 C20 Ethers Linear and cyclic V2. oxalic acid Oxidizable with iodine: ascorbic acid V2. V4 C20 Mercaptans V0. e.C22 V16 C0 V10 C0 Nitrocompounds V3. diphenylmethanol Weakly basic pKa >8: Imidazole. carbazole Strongly basic: aminopyridine Reaction with methanol: naphthylamine. toluidine Oxidizable with iodine: aminophenol Method V2.V8 C20 V10. V3.V3 C20 di-Nitrobenzene. anisidine. cresol. V4 C20 V2 C20 Substance Halogenated hydrocarbons Isocyanates Ketones Examples R-Cl. V4 C20 V15 C20 V0.

ZnSO4 V2. NaAsO2 KHCO3 . V31 C20. Na2HPO4 tert. creams Suppositories Tablets Lyophilized preparations V2 V4. V32 C20. MgCl2 Cu(I) salts: CuCl2 NaH2PO4 . C32 V31 C32 Sulfates Silicon compounds Substance Phosphates Examples Method V2. Phosphate. indicator dyes. Silicon dioxide Silanols R3Si(OH) Na2SO4.: Na3PO4 Silicon oxide. V8 Cosmetics Creams.g. poly-amides. 78 . V30 Insecticides. C34 V2.C40 V2 Adhesives All-purpose glue. V32 C20. V5 V5 V2 V20 V2 V5 V30. oxides Halogenides Examples Method V30 C30 V34 C32 V31 C32 V21. e.1. C34 V2. bitumen lubricating grease. C32 V31 C32 Thiosulfates Tin(II)salts Na2S2O3. ski wax Tar. glue stick Rubber cement Textile auxiliaries Surfactants powder optical brightener Plastics Polymers Polyethylene. fungicides. HBO3 . dispersion dyes Waxes. V31 C31. paraffins: shoepolish. V32 C21. KJ. H3BO3 NaOH. CaO NaCl. CaCl2 . lotion Lipstick Soaps Toothpaste V4.1. etc. NaHCO3 Na2CO3 B2O3 . V31 C32 V2. V32 C21. disinfectants Salves. C32 Pharmaceuticals Antibiotics. KOH MgO. Insoluble: pigments. NH4NO3 Nitrites NaNO2 11.2 Inorganic chemicals Substance Arsenic compounds Bicarbonates carbonates Boron compounds Hydroxides. multipurpose grease V2 V2. C34 V31 C33 V2. herbicides Soluble: wool dyes. V31 C20. etc. polyurethane. C32 V15. V31 C20. V5 V12 V2 V40.3 Technical products – organic Substance Agrochemicals Dyes Examples Method V2 Substance Petrochemicals Examples Method V12 C0 V7 V5. NaSO3 Na2S2O5 SnCl2 Nitrates NaNO3 . PVC. C34 V10 Na2HAsO3 . polystyrene. polypropylene.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.

potato chips Potato flakes Dough. Zwieback Yogurt. sea salt Total water: plain salt. wood Cellulose powder Wool. C30 V2 V20 Paper. (V5) V6 C23 V32 C34 V8 V2 V6 V5 79 .almonds instant coffee Fats Butter. mixed spice Mustard Adherent moisture: plain salt. instant coffee. noodles. meat spread. perborates) without brightener Total water V30 V2 11. Zwieback. (V25) V22. broth Biscuits. corn. mayonnaise Shortening.1.inorganic Substance Building materials Fertilizers Examples Method V32 (C34) V6 Substance Minerals Detergents Examples Method V32 V30. wheat. V23 Cacao. tobacco. plaster. cement Adherent moisture Zeolites Laundry detergent with brightener (hydroxides. ice cream Dried albumen Powdered milk V2 V13 V2. V23 Vegetable products V22.6 Food Substance Protein products Examples Method V23 Substance Grains and starchy foods Examples Method V13. almond paste Instant ice tea. dried vegetables and fruits Hazelnuts. margerine.4 Technical products .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. jam Honey. rye. coffee beans. (V30) Cheese. curry.1. candy. noodles. V21 Mortar. silk 11. V5 V5 Sugar and sugar products V13 V13 Sugar: total water cont.1. sea salt V23 V24. pudding powder.5 Technical natural products Substance Cellulose products Fibrous materials Examples Method V30. jellied fruits. hardened fat V4. gummi bears. tea. caramel. V23 V30.. jelly Sugar: adherent moisture Chocolate Spices Pepper.

1 Organic and inorganic chemicals Substance Acetals Examples Method V1 C1 Substance Hydrocarbons Examples Method V1 C1 Acetal. isobutane. t-butyl chloride. chlorotoluene Acetone. cyclohexane. C1 Sulfurcompounds V1 C1 V0. dioxane. acetophenone. acrylic acid V15 C0 V1 C1 V1 C1 V1 C1 V1 C1 Acid amides Dimethylformamide Sulfides. dodecane > C14 heavy oil. methylal C1 to C7 hexane. pentane. anisole Methyl benzoate. benzaldehyde V11 C0 saturated and unsaturated V4 C1 Alcohols Propanol. acetic acid > C2 propionic acid.2 Liquid samples 11.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. xylene C7 to C14 gasoline. hydroxylamine V1 C1 V1 C1 Mineral acids V5 C30 V15 C0 Amines H2SO4. HNO3. paraffin Aldehyde Acetaldehyde. hexanol. methylethylketone Ketones V10 C10 80 . hexylamine Reaction with methanol: aniline. ethylal. petroleum. diamine Easily oxidized with iodine: hydrazine. C0 Ethers Esters Halogenated hydrocarbons Dimethylether. chinoline Strongly basic: alihatic amines N-butylamine. toluene. nitrochlorobenzene Acetonitrile V16 C0 Nitrocompounds V1 C1 V10 C0 Nitriles V1 C1 V0 C0 Peroxides H2O2 V15 Carboxylic acids C1 to C2 formic acid. crude oil. toluidine. benzene. HCl Nitrobenzene. disulfides sulfonic acids Mercaptans V1. nitrotoluene. ethyl acetate Methyl chloride.2. cyclohexene. benzyl alcohol Weakly basic: N-methyl aniline heterocyclic amines pyridine. chlorobenzene.

wine. sample input and titration methods.2. massage oil Vegetable oils Technical oils Hydraulic oil.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. silicon oil Motor oils V5 C1 V30 C30 For more details on the sample preparation. liquor Pharmaceuticals: extrakts. sunflower oil Pharmaceuticals and cosmetics: ethereal oils.3. shampoo Method V1 V1 V1 V1 V4 Tensides and detergents Aqueous emulsions Milk products: milk. fungicides Acrylic enamels Emulsions in solvents V1 V1 V29 V4 C1 V7 V4 C1 V4 C1 Agrochemicals (sprays): insecticides Synthetic enamels Foods: salad oil. refer to chapter 11. condensed milk Tensides and detergents Agrochemicals (sprays): herbicides. brake fluid. cream.2 Foods and technical products Substance Aqueous solutions Examples Foods: spiced sauce: soy sauce beverages: beer. 81 . tinctures Cosmetics: perfume. transformer oil.

120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / chloroform 1:5 Stir time: 60 .120 s Delay time: 7 seconds.120 s V2 V3 Direct titration with added 2-propanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / propanol 1:1 Stir time: 60 .10 minutes V4 V5 V6 V7 V8 V10 V11 V12 82 .3.10 minutes Direct titration methanol free Titrant: two comp.120 s Direct titration with added formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 5 .120 s Direct titration with added 1-decanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / 1-decanol 1:1 Stir time: 60 .1 Volumetric methods The methods have been developed using 2-component reagents. Direct titration with added toluene Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / toluene 1:1 Stir time: 60 . These can be also performed using the one-component reagent. dProcedure V1 Direct titration Titrant: Solvent: Stir time: Direct titration Titrant: Solvent: Stir time: two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 10 s two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 60 . In this case methanol is used as a solvent.120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: KF solvent / chloroform 1:1 to 1:2 Stir time: 60 . reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Start immediately (autostart) Direct titration with heat (at 50°C) Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent Stir time: 5 . reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Stir time: 30 – 60 s Direct titration methanol free Titrant: two comp.3 Titration Methods 11.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.

METTLER TOLEDO Good Titration PracticeTM in KF Titration V13 Direct titration with added formamide and heat. Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with methanol at 50 °C Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide 1:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide/methanol 8:2:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 With drying oven at 110 .220°C Titrant: two component reagent 5 or 2mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .20 min Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated solvent and inject entire solution into titration cell and titrate.15 minutes Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 20 mL buffer or 7g imidazole Stir time: 60 . 50°C Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 10 .120 s Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 5 g benzoic acid Stir time: 1-2 minutes External extraction with methanol at room temperature Titrant: two component reagent 5 mgH2O/mL Solvent: 30 mL KF solvent External extraction with methanol at room temperature in sonicator Remove aliquots of extraction solution over membrane filter with syringe.150°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 . Titrant: two component reagent 2 mg H2O/mL Solvent: 50 mL KF solvent Side reaction: KF titration not possible V15 V16 V20 V21 V22 V23 V24 V25 V29 V30 V31 V32 V40 V0 83 .20 min With drying oven at 160 .20 min With drying oven at 300°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .

Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with 1-decanol or external dissolution in 1-decanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with chloroform or external dissolution in chloroform Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction or external dissolution in chloroform (methanol free) Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones With drying oven at 110-130°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 140-150°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 160-190°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 200-250°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 300°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated anolyte and inject entire solution into titration cell and titrate. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Coulometric determination not possible C10 C20 C21 C22 C23 C24 C30 C31 C32 C33 C34 C40 C0 84 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.3.2 Coulometric methods Method C1 Procedure Direct titration Anolyte: Catholyte: 100 mL anode reagent 5 mL cathode reagent C5 Direct titration with added chloroform Anolyte: 70 mL anode reagent and 30 mL chloroform Catholyte: 5 mL cathode reagent Direct titration methanol free Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones External extraction with methanol or external dissolution in methanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with Methanol in sonicator Remove aliquots of extraction solution over membrane filter with syringe.

formamide). SiO2 Salts. (Select stir time so that sample dissolves completely. 1-decanol. Pulverize with mortar. (Pre-heat syringe with hair dryer or in drying oven.8 mm S11 S12 syringe without needle (Fill very thick samples in back of syringe) weighing boat 85 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. Let solids settle and remove aliquot of remaining solution with syringe. S3 S2. Zwieback Dried vegetables and fruits. honey. pastes Pulverized soluble Salves. Cut in small pieces with scissors or knife. shoepolish Creams. bitumen Method S7. or up to approx. Stir. for very thick pastes drill hole in bottom of syringe.g. formamide). margarine Phenols. yogurt Salts. silk Cheese.5 mm or without needle. resinous Waxes Examples Butter.4 Sample preparation and input 11. After sample removal keep sample sealed. At room temp. S11 S4. pepper. Use syringe with needle Ø 1. shake or sonicate. chocolate Method S1 S1. cristalline products Wheat. Dissolve sample or extract water. 1-decanol.4. S2 S1. tobacco. coffee. napthalene. almonds. S10 S2. S11 S6. brittle Hard natural products Fibrous natural products Tenacious products Soft products Hard. greasy Examples Minerals.1 Solids: Characteristics Property Very hard Hard. Use grate to reduce size. S10 S11 S10.: CaCO3 .4. Pulverize with mixer.g. S3 S10. S5 S10 S8 Paraffins. jelly. noodles. Press through small holes e.) S8 S9 S10 syringe with needle Ø 0. S8 S10 Property Soft. meat Jellied fruits. the moisture will be pressed out with pre-heated syringe (with needle Ø 0.) Homogenize sample well. creams gel. S10 S11 S4. tea. brittle Soft.2 Solids: Sample input Method S1 S2 S3 S4 S5 S6 S7 Sample input finely ground sample with weighing boat finely ground sample with weighing boat finely ground sample with weighing boat with spatula with spatula or weighing boat with spatula or weighing boat with spatula Do not use syringe. 60° C. Inject into titration cell.8 mm ) Fill in backend of syringe Procedure Grind in sealed. cooled analysis mill. rocks e. wool. almond paste. Melt sample. ice cream. paper. potato flakes Tar. gummi bears. active ingredients Na-tartrate S9 S12 11. After sample removal keep sample sealed. broth Hardened fat. No further preparation necessary. greasy Soft. In external extraction solvent (methanol. Break and disperse with high-speed mixer (up to 24000 cpm) in external extraction solvent (methanol. meat grinder. Homogenize sample well.

The pressure loss during sample removal must be compensated with dried air.15 °C .8 mm ME-71482 ME-71484 Septum NS24 ME-23950 Three-hole adapter ME-23982 86 . gasoline.4. . Hygroscopic sample or low moisture content (< 1000 ppm) . . aqueous emulsions Acrylic enamels. .3 Liquids: Characteristics Property Liquid Turbid Low boiling point Hygroscopic Low moisture content Non-hygroscopic. .Remove sample immediately. acetone.Inject sample into titration cell through septum or needle hole of three-hole adapter with 10 mL syringe (with needle Ø 0.8 mm) Inhomogeneous emulsions . For each titration use 1 mL syringe (with needle Ø 0.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.5 mm) Injection with syringe after cooling sample (with needle Ø 0. crude oil.Keep sample in a septum flask. toluene. salad oil Perfume.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. H2SO4.8 mm) to remove fresh sample from sample flask and inject this into titration cell through septum or needle hole of three-hole adapter. glass Visco-Spoon™ 1 mL ME-71492 1.Homogenize thoroughly by shaking or stirring prior to sample removal.8 mm).8 mm) Injection with syringe (without or with needle Ø 1.Cool sample to approx.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. .2 mm ME-71483 ME-23951 ME-51107668 10 mL 0. . acetic acid Silicon oil.Rinse syringe with sample 2-3 times (pull up and discard) and condition for 5 minutes. 11. milk. cream Method L1 L2 L3 L4 L4 L1 L5 L6 11. L2 L3 L4 L5 Injection with syringe L6 Injection with syringe after sample homogenization (with needle Ø 0. acetone. Boiling point 5 .4. Samples with high moisture content (> 50%) Rinse syringe with sample 2-3 times. after-shave Beverages.15°C Examples Propanol. 0°C in ice bath. detergents.8 mm) Injection with syringe Procedure Fluid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. glycerine Acetaldehyde Methanol.5 Accessories for sample input Syringe Injection needle Weighing boat. Turbid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.4. synthetic enamels.4 Liquids: Sample input Method L1 Sample input Injection with syringe (with needle Ø 0. glycerine Hexane. petroleum. average moisture content High moisture content Inhomogeneous (> 50%) (< 1000 ppm) 5 .

Anal. S. 395-403 (1977).S. . J. Soc. Rotating ring disk electrode meassurement“. Chem. 334. A. HOPFKINSON..6 References [1] [2] FISCHER. Liebigs Ann.C. Anal. Chem. G. “Mechanism and reaction rate of the Karl Fischer titration reaction. J. Anal. [3] [4] [5] [6] [7] 87 . M. GRÜNKE.. “Reaktionsmechanismen in der Karl-Fischer-Lösung“. BARENDRECHT. J. 86.. VERHOFF. Zweikomponenten Reagentien mit Imidazol“. SMITH. Part I.. “Analytical Procedures Employing Karl Fischer Reagent I. Both publications from: SEUBERT.396 (1935).C. Chem. First and second order catalytic currents at a rotating disk electrode“. „Mechanism and reaction rate of the Karl Fischer titration reaction.. Chem. PhD. SEUBERT A. Electroanal.. Anal. Fresenius Z. F. 30-32 (1981).. COFINO. 460-464 (1982). 394 . „Kinetics and stoichiometry in the Karl Fischer solution“. Verlag Chemie Weinheim (1954) / (in German). Chem 368. Anal. Electroanal. 305-315 (1976).. „Karl-Fischer Reagentien ohne Pyridin. Chim. Chem.C. „The Dead-Stop End Point – As Applied to the Karl Fischer Method for Determining Moisture“. Fresenius Z. S. G. Chem.. 256-260 (1989) (in German). G. MITCHELL jr. Part II.. “Mechanism and reaction rate of the Karl Fischer titration reaction. Eng. BARENDRECHT. SCHOLZ. 75. „Karl-Fischer Reagentien ohne Pyridin. Chem. E. 71... W. Chem. Auflage. 303.. E. Fresenius Z.. Diploma-Thesis at the University of Hannover / Germany.C. WÜNSCH. VERHOFF. Potentiometric measurements”. KOK. 312. Fresenius Z.2412 (1939).C... VERHOFF. Part III. Thesis University of Hannover. C. [10] GRÜNKE. 1. K. J. “Determination of Water by Titration with Coulometrically Generated Karl Fischer Reagents”. Ind. SEUBERT A. 86. Rotating ring disk electrode meassurement .. D.. 705-717 (1976). Anal. W. Ed. 75-80 (1978).. 309. Acta. J. 306. J... BUNSEN. “Mechanism and reaction rate of the Karl Fischer titration reaction. Chem.. Chem. SCHOLZ. WÜNSCH. E. “Stöchiometrie und Kinetik der Karl-Fischer –Reaktion in Methanol als Reaktionsmedium”. Chem.. SCHOLZ. 272 – 274 (1943). Analytical implications”. Electroanal. E. Th. “Untersuchungen zur Karl-Fischer-Reaktion”. Anal.M. E. Anal. 15 (4). [8] SCHOLZ. M. 394 . J.. 16-21 (1989) (in German). 309. 1988 (in German). E. Angew. 93. Z. WERNIMONT. Chem. Anal.W. Anal. Z. Fres. 334. Chem.. Neue Eichsubstanzen“. 31 (2). BOYD.comparison with the aqueous system“. VERHOFF. See literature references in: EBERIUS.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. G. 215 – 219 (1959).4. 407-415 (1978). VERHOFF. BARENDRECHT. P. 94. “Mechanism and reaction rate of the Karl Fischer titration reaction. E. Part IV. 1999 (in German). Amer.. „Wasserbestimmung mit Karl-Fischer-Lösung“. Chem. Nature of the Reagent”.207 (1980). “Karl-Fischer Reagentien ohne Pyridin“. Fres. [9] WÜNSCH. Fresenius J. “Nebenreaktionen in Karl-Fischer-Reagenzien ”. W. 2407 . Chem. Fresenius Z. E. J. Part V. MEYER. J.J. 48. 123-125 (1981). 265 (1853). J. 203 .. SCHOLZ. 61. „Karl-Fischer Reagentien ohne Pyridin. „Karl-Fischer Reagentien ohne Pyridin Genauigkeit der Wasserbestimmung“. E.396 (1981). „Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern“. Einkomponenten Reagentien“. A. BRYANT. Electroanal. J. Chem. R. Anal. 139-147 (2000).

. D. Springer Verlag Berlin. 2006. GIT Verlag GmbH.A. WIELAND. 1989 (German) 88 . 11.30918 Seelze / Germany.Theorie und Praxis“.. „Eugen Scholz Reagents for Karl FischerTitration“. „Karl Fischer Titration“. Food Chemistry 96.. DE CARO C. M. SCHÖFFSKI. "Coulometric Karl Fischer titration with a diaphragm-free cell: Cell design and applications"... E. RÜEGG K. 1985.. 431-435 (2006). Sigma-Aldrich Laborchemikalien GmbH. 1984. SCHOLZ. Darmstadt / Germany.METTLER TOLEDO Good Titration PracticeTM in KF Titration [11] LANZ. G. K.5 Additional literature HYDRANAL®-Manual. „Wasserbestimmung durch Karl-Fischer-Titration .. DE AGOSTINI A. „Untersuchungen einer Karl-Fischer-Reaktion“. Diploma-Thesis at the University of Hannover / Germany.

WP: This is what we get from the calculation in the KF method. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent C ⋅ msol + C ⋅ mext ⋅ R = R ⋅ mext + B ⋅ msol C ⋅ mext ⋅ R − R ⋅ mext = B ⋅ msol − C ⋅ msol R ⋅ (C ⋅ mext − mext ) = B ⋅ msol − C ⋅ msol R= 1 ⋅ (B ⋅ msol − C ⋅ msol ) (mext ⋅ (C − 1)) R= R= 1 ⋅ (C ⋅ msol − B ⋅ msol ) (mext ⋅ (1 − C )) since 1 1 =− 1− C C −1 1 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 1 − C ⎝ mext R (%) = 100 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 100 − C ⎝ mext since 1 = 100%. The sample P used for the extraction is not dissolved. 89 . For ppm : R (ppm ) = 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 10 6 − C ⎝ mext since 1 = 106 ppm. % or ppm).1 Formula for the external extraction Principle: • • The water amount (in grams) after extraction is equal to the water amount before extraction. WTOT : Water content of the supernatant extraction solvent (% or ppm) WL : mL : mP : Thus: 1) 2) 3) 4) 5) 6) 7) For % : C ⋅ [msol + (mext ⋅ R )] = R ⋅ mext + B ⋅ msol R C B msol mext Blank value (water content of the solvent. Water amount after extraction = Water amount before extraction WTOT•(mL + (mP•WP) ) = WP•mP + WL•mL where Water content in the sample P (% or ppm).METTLER TOLEDO Good Titration PracticeTM in KF Titration 12 Appendix 12.

Water amount after dissolution = Water amount before before dissolution WTOT•(mL + mP) = WP•mP + WL•mL where WP: WTOT : WL : mL : mP : Thus: 1) 2) 3) 4) C ⋅ [msol + mext ] = R ⋅ mext + B ⋅ msol Water content in the sample P (% or ppm) This is what we get from the calculation in the KF method. the total volume is increased.1% SIGMA-ALDRICH HYDRANAL®-Water Standard 0. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ 12.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12.2 Formula for the external dissolution Principle: The water amount (in grams) determined by titration is the sum of the water amounts present in the solvent and in the sample.1 mg/g (100 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 1. Blank value (water content in% or ppm) of the solvent. Total water content (sample + solvent).01% VWR/VWR/MERCK APURA water standard 0.55% (potassium citrate monohydrate) The water content is declared on a test certificate supplied with every vial. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent R C B msol mext C ⋅ msol + C ⋅ mext = R ⋅ mext + B ⋅ msol R ⋅ mext = C ⋅ msol + C ⋅ mext − B ⋅ msol ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R = C ⋅⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % and ppm: ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%.00 mg/g (1000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5. 90 . The sample P used for the external dissolution is completely dissolved into the solvent.3 Standards for Karl Fischer coulometry a) For direct measurements: VWR/VWR/MERCK APURA water standard 0. in % or ppm. Thus.

Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. If the sample does not completely dissolve. In this case. etc. nitrocompounds. acetamide.4. the sample must completely dissolve in the anolyte.4 Reagents and solvents for coulometric analysis To determine its total water content.4. esters. 30% hexanol APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% hexanol catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit For cells without diaphragm: 91 . ethers. edible oils. This is limited to a maximum of 30% to prevent the conductivity from falling too low. the anolyte must be immediately replaced. i. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Ethanol-based reagents: anolyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) Methanol-based reagents: electrolyte:HYDRANAL® Coulomat AD (SIGMA-ALDRICH) - For cells without diaphragm: - APURA combiCoulomat fritless (VWR/VWR/MERCK) 12. an emulsion is formed. alcohols. 12. ointments. etc. This means that if an emulsion is formed in the anolyte.1 For samples that are soluble in methanol or ethanol These include: hydrocarbons (up to C10). part of the water content is not measured. the water content determined is lower than the actual water content of the sample. Alternatively. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG-H (SIGMA-ALDRICH) contains approx.e. hydrocarbons (C10 to C20).2 For samples that are poorely soluble in methanol or ethanol These include: etherial oils. chlorinated hydrocarbons (up to C10).METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. more solvent can be added to the anolyte. A number of different anolytes are available to dissolve the various types of samples encountered in practice.

4. For cells without diaphragm: - Notes on ketones: - - 92 . For cells with diaphragm: Methanol-free reagents: anolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat CG-K (SIGMA-ALDRICH) Methanol-free reagents: electrolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) When changing from normal KF anolytes to ketone reagents. hydrocarbons (above C20).METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 20% hexanol APURA CombiCoulomat fritless (VWR/VWR/MERCK) + 20% hexanol 12.3 For samples that are insoluble in methanol or ethanol These include: petroleum oils. transformer oils. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat A (SIGMA-ALDRICH) + 20% chloroform HYDRANAL® Coulomat AG (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% chloroform catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat fritless (VWR/VWR/MERCK) + 30% chloroform For cells without diaphragm: - 12. etc.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal or an acetal and water.4. Chloroform must be added to the anolyte to ensure the solubility of these samples. This is limited to a maximum of 30% in order to prevent the conductivity from becoming too low. we recommend the use of a second titration cell. silicone oils. the entire titration cell must be thoroughly cleaned because even traces of methanol may cause serious interferences. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → (CH3)2CO + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O Special methanol-free reagents must be used for these substances. If you measure ketones regularly.

g.2 mL to 0. Fill the anode compartment with approx. easily be measured with volumetric KF determination. In these cases the pH value of the anolyte should be measured.g.4. formic acid. benzaldehyde) can also be determined by coulometric KF titration. The measurement should not be performed in the titration cell because the electrode introduces too much water. i.e.5 mL. 80 mL of anolyte and 20 mL HYDRANAL® buffer. it is possible that the anolyte is exhausted after a few days even though no further titrations have been performed. with reactive ketones such as cyclohexanone use only 0. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. The larger the sample. After a longer standby period. the more important the effect of side reactions becomes. Choose relatively small samples (approx. acetaldehyde) are oxidized at the anode with the formation of water. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes.2).5 to 7 (see Section 1. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. Basic samples must be neutralized with salicylic acid or benzoic acid. the drift is higher because of the very slow side reaction. the substances can. Short chain aldehydes (e. Coulometric KF titration cannot be used to determine these compounds. The use of imidazole increases the pH value in the anolyte.g. etc. however. - - Notes on aldehydes: - - 12.g. Fill the anode compartment with approx. Use the HYDRANAL® buffer (SIGMA-ALDRICH). e. e. - For acidic samples. 1 mL).5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. amines: - 93 .METTLER TOLEDO Good Titration PracticeTM in KF Titration - If you have titrated a number of ketone samples. The special reagent for ketones can also be used for other samples. It is important to note that alcohols that react with ketones should not be titrated in this reagent. Measure the pH with a glass electrode adjusted with aqueous buffers. Aromatic aldehydes (e. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). 90 mL of anolyte and 5 g salicylic acid or benzoic acid. take an aliquot of anolyte from the titration cell. the pH value of the anolyte must be adjusted to the range 5.: - For basic samples. acetic acid. With Karl Fischer titrations of acidic and basic samples. To do this.

ointments. an emulsion is formed. If it does not completely dissolve. One-component reagents: 94 . i.0 mg/g (1000 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 10. the anolyte must be immediately replaced.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. A number of different anolytes are available to dissolve the various types of samples encountered in practice.1% VWR/VWR/MERCK APURA® water standard 1% SIGMA-ALDRICH HYDRANAL®-Water Standard 1. ethers. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: Dry methanol Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent Ethanol-based: Titrant: HYDRANAL® Titrant E Solvent: HYDRANAL® Solvent E (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: (SIGMA-ALDRICH) (VWR/Merck) - (SIGMA-ALDRICH) (SIGMA-ALDRICH) 12.6 Titrants and solvents for volumetric analysis The sample must be completely dissolved in the anolyte to determine the total water content. alcohols. The water content is declared on a test certificate supplied with every vial. This is limited to a maximum of 50%.6.55% (potassium citrate monohydrate). 12. In this case. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. acetamide.0 mg/g (10’000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5.6. In this case. esters.1 For samples soluble in methanol or ethanol These include: hydrocarbons (to C10). Alternatively. part of the water content is not measured. more solvent can be added to the anolyte 12. etc.5 Water Standards for Karl Fischer volumetric titration a) For direct measurements: VWR/VWR/VWR/MERCK APURA® water standard 0. hydrocarbons (C10 to C20). chlorinated hydrocarbons (to C10). nitrocompounds. etc. edible oils. the result determined is lower than the actual water content.e.2 For samples poorly soluble in methanol or ethanol These include: etherial oils.

3 For samples insoluble in methanol or ethanol These include: petroleum oils. This is limited to a maximum of 50% in order to prevent the conductivity from becoming too low.6.6. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® Solver (Crude) apura® CombiSolvent Fats Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM. with the formation of water. silicone oils.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® LipoSolver CM. One-component reagents: 95 . or an acetal. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (VWR/Merck) Two-component reagents: - (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. Chloroform must be added to the anolyte to ensure the solubility of these samples. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O (CH3)2CO + 2 CH3OH → Special methanol-free reagents must be used for these substances. etc. MH apura® CombiSolvent Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal. transformer oils. hydrocarbons (above C20). Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12.

If you have titrated a number of ketone samples. The special reagent for ketones can also be used for other samples.2 mL to 0.2).e. It is important to note that alcohols that react with ketones should not be titrated in this reagent. Use the HYDRANAL® buffer (SIGMA-ALDRICH). the more important the effect of side reactions becomes.5 mL.g. the entire titration cell must be thoroughly cleaned because even traces of methanol can cause serious interference. Choose relatively small samples (approx. the drift is higher because of the very slow side reaction.g. acetic acid. With Karl Fischer titrations of acidic and basic samples. If you measure ketones regularly. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult.5 to 7 (see Section 1. Measure the pH with a glass electrode adjusted with aqueous buffers.g. i. Aromatic aldehydes (e. Short chain aldehydes (e. To do this. acetaldehyde) are oxidized at the anode with the formation of water. 1 mL). It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes. e. benzaldehyde) can also be determined by coulometric KF titration. Coulometric KF titration cannot be used to determine these compounds. etc. however. the substances can.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-free: Titrant: Solvent: HYDRANAL® Composite 5 K apura® CombiTitrant 5 Keto (SIGMA-ALDRICH) (VWR/Merck) HYDRANAL® Medium K (SIGMA-ALDRICH) HYDRANAL® Working Medium K HYDRANAL® KetoSolver apura® CombiSolvent Keto (VWR/Merck) Notes on ketones: When changing to ketone reagents. take an aliquot of anolyte from the titration cell.6. we recommend the use of a second titration cell. 80 mL of anolyte and 20 mL HYDRANAL® buffer.g. Fill the anode compartment with approx. The larger the sample. amines: 96 . Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. easily be measured with volumetric KF determination. e. The measurement should not be performed in the titration cell because the electrode introduces too much water. - For acidic samples. with reactive ketones such as cyclohexanone use only 0. the pH value of the anolyte must be adjusted to the range 5.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift.: - For basic samples. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). The use of imidazole leads to a high pH value in the anolyte. - Notes on aldehydes: - - 12. formic acid. In these cases the pH value of the anolyte should be measured.

4 Safety data for the KF-components and auxiliary solvents: sulfur dioxide: iodine: diethyleneglycolmonomethylether: 2-methoxyethanol: MAK-value: 200 ppm MAK-value: 0. Do not let reagent contact skin or eyes.: 28 °C MAK value: 100 ppm Flammable. swallowed or allowed to contact skin.: 11 °C MAK value: 200 ppm Highly flammable. Irritant when inhaled. Safety: flammable to extremely flammable. Ignition temp. buffer (imidazole) and solvent (methanol. Ignition temp.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Basic samples must be neutralized with salicylic acid or benzoic acid. Health hazard when inhaled.3 Reagents for coulometry: Composition: iodine.: 46 °C MAK value: 5 ppm Flammable. Do not let reagent contact skin or eyes. 2methoxyethanol or diethyleneglycolmonomethylether). Disposal: as an organic solvent. 13 Hazards and waste disposal tips 13. and solvent (methanol.2 Two-component reagent: Composition: iodine and solvent (methanol. Fill the anode compartment with approx.: does not burn MAK vlaue: 200 ppm 97 methanol: o-xylene: chloroform: . Ignition temp. Keep container tightly closed. Keep away from open flames or sparks. xylene or trichloroethaylene). buffer (imidazole) and solvent (methanol. 2-methoxyethanol). poisonous when inhaled or swallowed. iodine. tetrachloromethane.: 87 °C Ignition temp. Disposal: as an organic solvent. oxidant Ignition temp. 13. Disposal: as an organic solvent. Irritant when inhaled. Keep away from open flames or sparks. Keep container tightly closed and far removed from open flames or sparks. Irritant when inhaled. The KF solvent contains: sulfur dioxide. chloroform. buffer (imidazole). Skin irritant. 2-methoxyethanol. sulfur dioxide.1 ppm. Health hazard upon inhalation. Do not let reagent contact skin or eyes. Keep container tightly closed. 2methoxyethanol or diethyleneglycolmonomethylether). 13. swallowed or allowed to contact skin.1 One-component reagent Composition: sulfur dioxide. swallowed or allowed to contact skin. Potential teratogen. Poisonous when inhaled or swallowed. Safety: Highly flammable. Safety: flammable to extremely flammable. Health hazard when inhaled. Health hazard when inhaled. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. 13.

Irreversible damage possible. Health hazard upon inhalation 98 . Ignition temp. Ignition temp.: inflammable MAK value: 20 ppm Irritant for skin and eyes. Potential teratogen.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1-decanol: formamide: toluene: Health hazard when inhaled. Ignition temp.: 95 °C Irritant for skin and eyes.: 6°C MAK value: 20 ppm Extremely flammable.

.

.

mt. are two powerful tools which are meant to facilitate your daily water determination analyses and to contribute to reliable results over the whole lifetime of your instrument. Analytical Sonnenbergstrasse 74 CH-8606 Schwerzenbach. It outlines specific aspects in developing and maintaining a good routine operation with METTLER TOLEDO Compact Coulometric and Volumetric KF as well as Excellence titrators. method validation. Routine operation including PQ. ©09/2009 Mettler-Toledo AG Printed in Switzerland. Evaluation of the appropriate titration system (DQ) i.Good Titration Practice in water determination Good Titration Practice™ (GTP) in general encompasses three important steps: 1. www.com For more information Mettler-Toledo AG. This brochure specifically focuses on Good Titration Practice in water determination using coulometric and volumetric Karl Fischer Titration. ME-51725145A Markt Support AnaChem . evaluation. development of SOPs and maintenance of the validated state of the analytical system. +41-44 806 77 11 Fax +41-44 806 73 50 Subject to technical changes. Switzerland Tel. The GTP KF brochure and the application brochure 38 containing dedicated applications on samples from various industry segments. specification of the analytical requirements and purchase decision 2. Installation of the selected analytical system comprising IQ and OQ and training of personnel 3.e.

Sign up to vote on this title
UsefulNot useful